KR20100012828A - Oxime compound and resist composition containing the same - Google Patents

Abstract

The present invention relates to an oxime compound represented by formula (I), and a resist composition comprising the same:

Wherein Y represents an unsubstituted or substituted n-valent C6-C14 aromatic hydrocarbon group, n represents an integer of 1 to 6, R ¹ represents a C1-C30 aliphatic hydrocarbon group or the like , R ² represents a linear or branched chain C1-C20 aliphatic hydrocarbon group and the like, W ¹ represents -CO-O- and the like, Q ¹ and Q ² are each independently a fluorine atom or the like Z represents a C1-C20 halogenated aliphatic hydrocarbon group and the like.

Description

OXIM COMPOUND AND RESIST COMPOSITION COMPRISING THE SAME

The present invention relates to an oxime compound and a resist composition comprising the same.

WO 2004/074242 A2 discloses oxime compounds with perfluoroalkylsulfonyloxy groups, which are used as acid generators.

It is an object of the present invention to provide a novel oxime compound and a resist composition comprising the same.

The present invention relates to:

Oxime compound represented by <1> Formula (I):

Wherein Y represents an unsubstituted or substituted n-valent C6-C14 aromatic hydrocarbon group, n represents an integer from 1 to 6,

R ¹ has a C1-C30 aliphatic hydrocarbon group, a C6-C14 aromatic hydrocarbon group, a C4-C10 heteroaromatic hydrocarbon group, a C1-C20 alkyl group having a C6-C14 aromatic hydrocarbon group, or a C4-C10 heteroaromatic hydrocarbon group C1-C20 alkyl group, and at least one methylene group of the aliphatic hydrocarbon group to be replaced with -O-, -S-, -CO-, -CO-O-, -SO ₂ -or -N (R ^c )- And an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a heteroaromatic hydrocarbon group, and an alkyl group are hydroxyl group, acryloyloxy group, methacryloyloxy group, halogen atom, cyano group, -OR ² , -CO Substitute at least one selected from the group consisting of -OR ² , -O-CO-OR ² , -O-CO-R ² , -SO ₂ -OR ² , -O-SO ₂ -R ² and -SO ₂ R ² Can be,

R ² represents a linear or branched chain C 1 -C 20 aliphatic hydrocarbon group wherein at least one methylene group is -O-, -S-, -CO-, -CO-O- or -N (R ^c )-and it may be substituted with at least one selected from the group consisting of a hydroxyl group, acryloyloxy group and methacryloyloxy group,

R ^c represents a hydrogen atom or a linear or branched chain C 1 -C 4 aliphatic hydrocarbon group,

W represents -CO-O-, -CH ₂ O- or -CH ₂ O-CO-,

Q ¹ and Q ² each independently represent a fluorine atom or a C1-C6 perfluoroalkyl group,

Z represents a C1-C20 halogenated aliphatic hydrocarbon group, a C6-C14 halogenated aromatic hydrocarbon group, a cyano group, -CX ₂ -R ¹ or -CX ₂ -SO ₂ -R ¹ , and X represents a halogen atom or C1-C20 halogenated aliphatic hydrocarbon group;

<2> an oxime compound according to <1>, wherein n is 1;

<3> Oxime compound according to <1>, wherein the unsubstituted or substituted n-valent C6-C14 aromatic hydrocarbon group is an unsubstituted or substituted phenyl group, an unsubstituted or substituted naphthyl group, an unsubstituted or substituted A biphenyl group, an unsubstituted or substituted anthryl group, an unsubstituted or substituted fluorenyl group or an unsubstituted or substituted phenanthryl group;

<4> Oxime compound according to <1>, <2> or <3>, wherein Z is a C1-C20 halogenated aliphatic hydrocarbon group or a C6-C14 halogenated aromatic hydrocarbon group;

<5> The oxime compound according to any one of <1> to <4>, wherein Q ¹ and Q ² each independently represent a fluorine atom or a trifluoromethyl group;

<6> Oxime compound according to any one of <1> to <5>, wherein R ¹ represents a C1-C30 aliphatic hydrocarbon group, wherein at least one methylene group is -O-, -S- or -N (R ^c ) May be substituted with at least one selected from the group consisting of hydroxyl groups and halogen atoms;

<7> The oxime compound according to any one of <1> to <5>, wherein R ¹ is a C1-C30 aliphatic hydrocarbon group, wherein at least one methylene group is replaced with -CO-;

<8> The oxime compound according to any one of <1> to <5>, wherein R ¹ is a C1-C30 aliphatic hydrocarbon group having an acryloyloxy group or a methacryloyloxy group, and one of the aliphatic hydrocarbon groups The methylene group may be replaced with —O—, —S—, —N (R ^c ) —, —CO— or —CO—O—;

<9> Oxime compound according to <1>, wherein the oxime compound represented by formula (I) is an oxime compound represented by formula (III):

Here, Y ¹ is a C1-C20 aliphatic hydrocarbon group having a phenyl group, acryloyloxy group or methacryloyloxy group which may be substituted with a C1-C20 aliphatic hydrocarbon group having an acryloyloxy group or a methacryloyloxy group. C1-C20 aliphatic having a biphenyl group, acryloyloxy group or methacryloyloxy group which may be substituted with a C1-C20 aliphatic hydrocarbon group having a naphthyl group, acryloyloxy group or a methacryloyloxy group which may be substituted Having a fluorenyl group which may be substituted with a C1-C20 aliphatic hydrocarbon group having an anthryl group, an acryloyloxy group or a methacryloyloxy group which may be substituted with a hydrocarbon group, or an acryloyloxy group or a methacryloyloxy group A phenanthryl group which may be substituted with a C1-C20 aliphatic hydrocarbon group, and at least one methylene group of a C1-C20 aliphatic hydrocarbon group ^{-O-, -S-, -N (R c} ) -, -CO- , or may be replaced by -CO-O-, R ^c is a hydrogen atom or a linear or branched chain C1-C4 aliphatic monovalent hydrocarbon group ,

Z ¹ represents a C1-C20 halogenated aliphatic hydrocarbon group or a C6-C14 halogenated aromatic hydrocarbon group,

R ³ represents a C3-C30 monocyclic or polycyclic aliphatic hydrocarbon group, wherein one or more methylene groups can be replaced with -O- or -CO-, which can be substituted with a hydroxyl group,

R ⁴ represents a single bond or a C 1 -C 20 divalent aliphatic hydrocarbon group, wherein one or more methylene groups can be replaced with —O—, —S— or —N (R ^c ) —;

<10> Oxime compound according to <9>, wherein Y ¹ is a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, a fluorenyl group or a phenanthryl group;

<11> An oxime compound according to <9> or <10>, wherein R ³ is a C3-C30 monocyclic or polycyclic aliphatic hydrocarbon group, wherein at least one methylene group is replaced with -CO-;

<12> Oxime compound according to <1>, wherein the oxime compound represented by formula (I) is an oxime compound represented by formula (Va);

Wherein Y ² is an unsubstituted or substituted phenyl group, an unsubstituted or substituted naphthyl group, an unsubstituted or substituted biphenyl group, an unsubstituted or substituted anthryl group, an unsubstituted or substituted fluorenyl group Or an unsubstituted or substituted phenanthryl group,

Z ¹ represents a C1-C20 halogenated aliphatic hydrocarbon group or a C6-C14 halogenated aromatic hydrocarbon group,

R ⁵ represents a C1-C30 divalent aliphatic hydrocarbon group, wherein one or more methylene groups can be replaced with -O-, -S- or -N (R ^c )-, where R ^c is a hydrogen atom or a linear or branched A chain C1-C4 aliphatic hydrocarbon group,

R ⁶ represents a hydrogen atom or a methyl group,

W represents -CO-O-, -CH ₂ O- or -CH ₂ O-CO-, and

Q ¹ and Q ² each independently represent a fluorine atom or a C1-C6 perfluoroalkyl group;

<13> An oxime compound according to <12>, wherein Q ¹ and Q ² are fluorine atoms and W is —CO—O—;

<14> Oxime compound according to <12> or <13>, wherein R ⁵ is a C1-C20 divalent aliphatic hydrocarbon group, wherein at least one methylene group is -O-, -S- or -N (R ^c )- Can be replaced with;

<15> a polymer comprising a structural unit derived from an oxime compound according to any one of <12> to <14>;

<16> The polymer according to <15>, wherein the polymer has an acid-labile group in addition to the structural unit derived from an oxime compound according to any one of <12> to <14>. Including structural units;

A resist composition comprising a <17> resin and an oxime compound according to any one of <1> to <14>;

A resist composition comprising a <18> resin and a polymer according to <15> or <16>;

<19> The resist composition according to <17> or <18>, wherein the resin is a structure which is insoluble or poorly soluble in an aqueous alkali solution but is soluble in an aqueous alkali solution by the action of an acid and has an acid-labile group Resin containing units;

<20> a resin composition according to <17> or <18>, wherein the resin further comprises another acid generator;

<21> A method for producing an oxime compound represented by formula (I) comprising:

Wherein Y represents an unsubstituted or substituted n-valent C6-C14 aromatic hydrocarbon group, n represents an integer from 1 to 6,

R ¹ has a C1-C30 aliphatic hydrocarbon group, a C6-C14 aromatic hydrocarbon group, a C4-C10 heteroaromatic hydrocarbon group, a C1-C20 alkyl group having a C6-C14 aromatic hydrocarbon group or a C4-C10 heteroaromatic hydrocarbon group C1-C20 alkyl group, and at least one methylene group of the aliphatic hydrocarbon group to be replaced with -O-, -S-, -CO-, -CO-O-, -SO ₂ -or -N (R ^c )- And an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a heteroaromatic hydrocarbon group, and an alkyl group are hydroxyl group, acryloyloxy group, methacryloyloxy group, halogen atom, cyano group, -OR ² , -CO Substitute at least one selected from the group consisting of -OR ² , -O-CO-OR ² , -O-CO-R ² , -SO ₂ -OR ² , -O-SO ₂ -R ² and -SO ₂ R ² Can be,

R ² represents a linear or branched chain C 1 -C 20 aliphatic hydrocarbon group, wherein at least one methylene group is to be replaced with -O-, -S-, -CO-, -CO-O- or -N (R ^c )- And it may be substituted with at least one selected from the group consisting of hydroxyl group, acryloyloxy group and methacryloyloxy group,

R ^c represents a hydrogen atom or a linear or branched chain C 1 -C 4 aliphatic hydrocarbon group,

W represents -CO-O-, -CH ₂ O- or -CH ₂ O-CO-,

Q ¹ and Q ² each independently represent a fluorine atom or a C1-C6 perfluoroalkyl group,

Z represents a C1-C20 halogenated aliphatic hydrocarbon group, a C6-C14 halogenated aromatic hydrocarbon group, a cyano group, -CX ₂ -R ¹ or -CX ₂ -SO ₂ -R ¹ , and X represents a halogen atom or C1-C20 halogenated aliphatic hydrocarbon group,

Compound represented by formula (VII) is:

Where Y, Z and n have the same meaning as described above,

 Reaction in the presence of a base with a compound represented by formula (VIII):

Where R ¹ , W, Q ¹ and Q ² have the same meanings as described above, and L represents a halogen atom.

Description of the Preferred Embodiments

In the oxime compound represented by formula (I) (hereinafter simply referred to as oxime (I)), Y represents an unsubstituted or substituted n-valent C6-C14 aromatic hydrocarbon group, and n represents an integer of 1 to 6 And n is preferably 1.

In this specification, the C6-C14 aromatic hydrocarbon group includes a fluorenyl group.

Examples of the unsubstituted n-valent C6-C14 aromatic hydrocarbon group include a phenyl group, 1-naphthyl group, 2-naphthyl group, 1,1'-biphenyl-4-yl group, 1-fluorenyl group and 2-flu Monovalent C6-C14 aromatic hydrocarbon groups such as orenyl group; Divalent C6-C14 aromatic hydrocarbon groups such as 1,4-phenylene group, 1,1'-biphenyl-4,4-diyl group and fluorene-2,6-diyl group; Trivalent C6-C14 aromatic hydrocarbon groups such as benzene-1,2,4-triyl group, naphthalene-2,3,6-triyl group and fluorene-2,4,6-triyl group; Tetravalent C6-C14 aromatic hydrocarbon groups such as fluorene-2,4,6,8-tetrayl group; And pentavalent C6-C14 aromatic hydrocarbon groups such as fluorene-2,3,5,6,8-pentyl group.

Examples of the substituent of the n-valent C6-C14 aromatic hydrocarbon group include halogen atoms such as fluorine atom and chlorine atom; C1-C6 alkyl groups such as methyl group, ethyl group and tert-butyl group; C6-C20 aryloxy groups such as phenoxy group; Cyano group; Nitro group; Hydroxyl group; C1-C20 hydroxyalkyl groups such as hydroxymethyl groups; And the following groups are included:

Wherein the straight line with the open end represents a bond in which adjacent n- extends from the C6-C14 aromatic hydrocarbon group.

A phenyl group, a biphenyl group, a fluorenyl group, a phenylene group, a biphenylene group, and a fluorenyl group are preferable, and a phenyl group and a phenylene group are more preferable.

In formula (I), R ¹ is a C1-C30 aliphatic hydrocarbon group, a C6-C14 aromatic hydrocarbon group, a C4-C10 heteroaromatic hydrocarbon group, a C1-C20 alkyl group having a C6-C14 aromatic hydrocarbon group or a C4- C1-C20 alkyl group having a C10 heteroaromatic hydrocarbon group.

Examples of the C1-C30 aliphatic hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 3 Tea-octyl, n-nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and isosilyl ( icosyl group, henicosyl group, docosyl group, docosyl group, tricosyl group, tricosyl group, pentacosyl group, hexacosyl group, heptacosyl group, octacosyl group, nonacosyl group and triacontile group linear C1-C30 aliphatic hydrocarbon groups such as triacontayl group; Branched C1-C30 aliphatic hydrocarbon groups such as isobutyl group, secondary-butyl group, tert-butyl group, methylpentyl group, ethylpentyl group, methylhexyl group, ethylhexyl group and propylhexyl group; Cyclic C3-C30 aliphatic hydrocarbon groups such as the following groups represented by formulas (R ¹ -1) to (R ¹ -16):

; And the following groups represented by formulas (R ¹ -17) to (R ¹ -41):

Among them, an aliphatic hydrocarbon group having a C1-C10 linear or branched aliphatic hydrocarbon group and a cyclohexyl group or adamantyl group is preferable, and a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group , Secondary-butyl group, tert-butyl group, ethylhexyl group, adamantyl group, cyclohexyl group, cyclohexylmethyl group and adamantylmethyl group are more preferable.

One or more methylene groups of the aliphatic hydrocarbon group may be replaced with -O-, -S-, -CO-, -CO-O-, -SO ₂ -or -N (R ^c )-, wherein R ^c is Hydrogen atom or a linear or branched chain C1-C4 aliphatic hydrocarbon group. Examples of linear or branched chain C 1 -C 4 aliphatic hydrocarbon groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and tert-butyl group. Examples of aliphatic hydrocarbon groups in which one or more methylene groups are replaced with —O—, —S—, —CO—, —CO—O—, —SO ₂ — or —N (R ^c ) — include formulas (R ¹ -42) The following groups represented by) to (R ¹ -60) are included:

The aliphatic hydrocarbon group described above is a hydroxyl group, acryloyloxy group, methacryloyloxy group, halogen atom, cyano group, -OR ² , -CO-OR ² , -O-CO-OR ² , -O-CO- _{^{R 2, -SO 2 -OR 2,}} -O-SO 2 -R 2 , and -SO may be substituted by at least one selected from the group consisting of R ² _2, where R ² is a linear or branched chain C1-C20 An aliphatic hydrocarbon group, wherein one or more methylene groups can be replaced with -O-, -S-, -CO-, -CO-O- or -N (R ^c )-, which is a hydroxyl group, acryl It may be substituted with at least one selected from the group consisting of a monooxy group and a methacryloyloxy group.

Hydroxyl group, acryloyloxy group, methacryloyloxy group, halogen atom, cyano group, -OR ² , -CO-OR ² , -O-CO-OR ² , -O-CO-R ² , -SO ₂ Examples of aliphatic hydrocarbon groups substituted with at least one selected from the group consisting of -OR ² , -O-SO ₂ -R ^2, and -SO ₂ R ² include formulas (R ¹ -61) to (R ¹ -182). The following groups shown are included:

The acryloyloxy group and the methacryloyloxy group are preferably each bonded to the terminal of the aliphatic hydrocarbon group. Examples of the C6-C14 aromatic hydrocarbon group include phenyl group, 2,4-dimethylphenyl group, 4-tert-butylphenyl group, 4-methylphenyl group, 1-naphthyl group and 2-naphthyl group. The aromatic hydrocarbon group is a hydroxyl group, acryloyloxy group, methacryloyloxy group, halogen atom, cyano group, -OR ² , -CO-OR ² , -O-CO-OR ² , -O-CO-R ² , -SO ₂ -OR ² , -O-SO ₂ -R ^2, and -SO ₂ R ² may be substituted with at least one selected from the group consisting of. Examples thereof include the following groups represented by formulas (R ¹ -183) to (R ¹ -189):

C4-C10 heteroaromatic hydrocarbon group, which is a hydroxyl group, acryloyloxy group, methacryloyloxy group, halogen atom, cyano group, -OR ² , -CO-OR ² , -O-CO-OR ² , ^{-O-CO-R 2, -SO} 2 -OR 2, -O-SO 2 -R 2 , and which may be substituted by at least one selected from the group consisting of -SO ^₂ R _2, for example, has the formula (R ¹ -190) to (R ¹ -195) include the following groups:

C1-C20 alkyl group having a C6-C14 aromatic hydrocarbon group, which is a hydroxyl group, acryloyloxy group, methacryloyloxy group, halogen atom, cyano group, -OR ² , -CO-OR ² , -O-CO And may be substituted with at least one selected from the group consisting of -OR ² , -O-CO-R ² , -SO ₂ -OR ² , -O-SO ₂ -R ^2, and -SO ₂ R ² , The following groups represented by formulas (R ¹ -196) to (R ¹ -213) are included:

C1-C20 alkyl group having C4-C10 heteroaromatic hydrocarbon group, which is a hydroxyl group, acryloyloxy group, methacryloyloxy group, halogen atom, cyano group, -OR ² , -CO-OR ² , -O- And may be substituted with at least one selected from the group consisting of CO-OR ² , -O-CO-R ² , -SO ₂ -OR ² , -O-SO ₂ -R ^2, and -SO ₂ R ² . , Including the following groups represented by formulas (R ¹ -214) to (R ¹ -221):

R ¹ is preferably a C1-C30 aliphatic hydrocarbon group, wherein one or more methylene groups may be replaced with -O-, -S- or -N (R ^c )-, which is composed of hydroxyl groups and halogen atoms It may be substituted with at least one selected from the group.

R ¹ is more preferably a C1-C30 aliphatic hydrocarbon group in which at least one methylene group is replaced by -CO-, or a C1-C30 aliphatic hydrocarbon group having an acryloyloxy group or a methacryloyloxy group, and a fatty One or more methylene groups of the aliphatic hydrocarbon group may be replaced with -O-, -S-, -N (R ^c )-, -CO- or -CO-O-.

In formula (I), W represents -CO-O-, -CH ₂ O- or -CH ₂ O-CO-, and W is preferably -CO-O-.

Q ¹ and Q ² each independently represent a fluorine atom or a C1-C6 perfluoroalkyl group. Examples of C1-C6 perfluoroalkyl group include trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, nonafluorobutyl group, undecafluoropentyl group and tridecafluorohexyl group, and Trifluoromethyl group is preferred. Q ¹ and Q ² are each independently preferably a fluorine atom or a trifluoromethyl group, and Q ¹ and Q ² are more preferably a fluorine atom.

Z represents a C1-C20 halogenated aliphatic hydrocarbon group, a C6-C14 halogenated aromatic hydrocarbon group, a cyano group, -CX ₂ -R ¹ or -CX ₂ -SO ₂ -R ¹ , and X represents a halogen atom or C1-C20 halogenated aliphatic hydrocarbon group. Examples thereof include trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, and the following:

Examples of -CX ₂ -R ¹ include:

Examples of -CX ₂ -SO ₂ -R ¹ include:

Z is preferably a C1-C20 fluorinated aliphatic hydrocarbon group or a cyano group.

Examples of the group represented by the following formula (Y) include:

The following groups represented by the formulas (Y-1) to (Y-87) are included:

Examples of oxime (I) include oxime compounds represented by formula (I), wherein the group represented by formula (Y) below is any one of the groups represented by formulas (Y-1) to (Y-87), Q ¹ and Q ² are fluorine atoms, W is -CO-O-, and R1 is methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, secondary-butyl group, tert-butyl Group, ethylhexyl group, adamantyl group, cyclohexyl group, cyclohexylmethyl group, adamantylmethyl group or any of the groups represented by the formulas (R ¹ -1) to (R ¹ -221).

As oxime (I), more preferred are oxime compounds represented by formula (III):

Wherein Y ¹ is substituted with a C1-C20 aliphatic hydrocarbon group having a phenyl group, acryloyloxy group or a methacryloyloxy group which may be substituted with a C1-C20 aliphatic hydrocarbon group having an acryloyloxy group or a methacryloyloxy group C1-C20 aliphatic hydrocarbons having a biphenyl group, acryloyloxy group or methacryloyloxy group which may be substituted with a C1-C20 aliphatic hydrocarbon group having a naphthyl group, acryloyloxy group or methacryloyloxy group which may be substituted. Fluorenyl group which may be substituted with C1-C20 aliphatic hydrocarbon group having an anthryl group, acryloyloxy group or methacryloyloxy group which may be substituted with a group, or C1 having an acryloyloxy group or methacryloyloxy group A phenanthryl group which may be substituted with a -C20 aliphatic hydrocarbon group, and at least one methylene group of the C1-C20 aliphatic hydrocarbon group May be substituted with -O-, -S-, -N (R ^c )-, -CO- or -CO-O-, R ^c has the same meaning as described above,

Z ¹ represents a C1-C20 halogenated aliphatic hydrocarbon group or a C6-C14 halogenated aromatic hydrocarbon group,

R ³ is a C3-C30 monocyclic or polycyclic aliphatic hydrocarbon group, wherein one or more methylene groups can be replaced with -O- or -CO-, which can be substituted with a hydroxyl group,

R ⁴ is a single bond or a C1-C20 divalent aliphatic hydrocarbon group, wherein one or more methylene groups can be replaced with —O—, —S— or —N (R ^c ) —.

Also preferred are oxime compounds represented by formula (Va):

Wherein Y ² is an unsubstituted or substituted phenyl group, an unsubstituted or substituted naphthyl group, an unsubstituted or substituted biphenyl group, an unsubstituted or substituted anthryl group, an unsubstituted or substituted fluorenyl group Or an unsubstituted or substituted phenanthryl group,

Z ¹ represents a C1-C20 halogenated aliphatic hydrocarbon group or a C6-C14 halogenated aromatic hydrocarbon group,

R ⁵ is a C1-C30 divalent aliphatic hydrocarbon group, wherein one or more methylene groups may be replaced with —O—, —S— or —N (R ^c ) —, wherein R ^c has the same meaning as described above,

R ⁶ represents a hydrogen atom or a methyl group,

W represents -CO-O-, -CH ₂ O- or -CH ₂ O-CO-, and

Q ¹ and Q ² have the same meaning as described above;

And an oxime compound represented by the formula (Va) wherein Q ¹ and Q ² are fluorine atoms and W is —CO—O—.

Oxime (I) is a compound represented by formula (VII):

Where Y, Z and n have the same meaning as described above,

With a compound represented by formula (VIII):

Wherein Q ¹ , Q ² , W and R ¹ have the same meaning as described above, and L is a halogen atom,

In an inert solvent such as toluene, tetrahydrofuran, N, N-dimethylformamide, dimethylsulfoxide, acetonitrile, chloroform and dichloromethane, in the presence of a base at about 0-150 ° C., preferably 0-100 ° C. It can be produced by reacting with stirring at temperature.

Examples of the halogen atom represented by L include fluorine atom, chlorine atom, bromine atom and iodine atom.

The amount of the compound represented by formula (VIII) is generally from 0.9n to 2n moles and preferably n to 1.5n moles per mole of the compound represented by formula (VII).

Examples of bases include inorganic bases such as sodium hydroxide, potassium hydroxide and potassium carbonate, and organic bases such as pyridine, triethylamine and lutidine. The amount of base is generally n to 3n moles and preferably n to 2n moles per mole of compound represented by formula (VII).

The oxime (I) obtained by the above method can be isolated by performing concentration followed by extraction, and the separated oxime (I) can be purified by recrystallization or column chromatography.

The compound represented by formula (VII) can be produced by the reaction of the corresponding ketone compound and hydroxylamine.

The compound represented by formula (VIII) is a compound represented by formula (VIIIa):

Where L, Q ¹ and Q ² have the same meaning as defined above,

It can be produced by the reaction of a compound represented by formula (VIIIb):

Where R ¹ has the same meaning as defined above.

Oxime (I), in which n is 1 and R ¹ is represented by the following formula:

Where R ⁵ and R ⁶ have the same meaning as defined above,

Compound represented by formula (X) is:

Where Y, Z, Q ¹ , Q ² , W and R ⁵ have the same meaning as defined above,

In the presence of a base in an inert solvent such as toluene, tetrahydrofuran, N, N-dimethylformamide, dimethylsulfoxide, acetonitrile, chloroform and dichloromethane together with acryloyl chloride or methacryloyl chloride It can be produced by reacting with stirring at a temperature of -100 to 150 ℃, preferably -20 to 50 ℃.

The amount of acryloyl chloride or methacryloyl chloride is generally 0.9 to 5 moles and preferably 1 to 1.5 moles per mole of the compound represented by formula (X).

Examples of bases include inorganic bases such as sodium hydroxide, potassium hydroxide and potassium carbonate and organic bases such as pyridine, triethylamine and lutidine. The amount of base is generally 1 to 5 moles and preferably 1 to 2 moles per mole of the compound represented by formula (X).

Oxime (I), in which n is 1 and R ¹ is represented by the following formula:

Where R ⁵ and R ⁶ are as defined above,

The compound represented by the formula (X) is composed of acrylic acid or methacrylic acid, chloroform, dichloromethane, dichloroethane, monochlorobenzene, acetone, methyl ethyl ketone, toluene, xylene, anisole, tetrahydrofuran, N, N-dimethylformamide And in an inert solvent such as dimethyl sulfoxide, it may be produced by reacting at a temperature of about -30 to 200 ° C, preferably -20 to 150 ° C in the presence of a dehydrating agent.

Examples of dehydrating agents include 1,1'-carbonyldiimidazole, N, N'-dicyclohexylcarbodiimide, 1-alkyl-2-halopyridinium salt, bis (2-oxo-3-oxazolidinyl) Phosphinic chloride (bis (2-oxo-3-oxazolidinyl) phosphinic chloride), 1-ethyl-3- (3-dimethylaminoprop) carbodiimide hydrochloride, di (2-pyridyl) carbonate, di (2-pyridylthionocarbonate) and 6-methyl-2-nitrobenzoic anhydride / 4- (dimethylamino) pyridine (catalyst) This includes.

The amount of acrylic acid or methacrylic acid is generally 0.5 to 5 moles and preferably 0.8 to 2 moles per mole of the compound represented by formula (X). The amount of hydrating agent is generally 1 to 3 moles and preferably 1 to 2 moles per mole of the compound represented by formula (X).

Oxime (I), in which n is 1 and R ¹ is represented by the following formula:

Where R ⁵ and R ⁶ have the same meaning as defined above,

Compound represented by formula (XI) is:

Where Y and Z have the same meaning as defined above,

With a compound represented by formula (XII):

Where L, Q ¹ , Q ² , W, R ⁵ and R ⁶ have the same meaning as defined above,

In an inert solvent such as toluene, tetrahydrofuran, N, N-dimethylformamide, dimethylsulfoxide, acetonitrile, chloroform and dichloromethane, in the presence of a base at about 0-150 ° C., preferably 0-100 ° C. It may also be produced by reacting with stirring at temperature.

The amount of the compound represented by formula (XII) is generally 0.9 to 2 mol and preferably 1 to 1.5 mol per mol of the compound represented by formula (XI). Examples of bases include inorganic bases such as sodium hydroxide, potassium hydroxide and potassium carbonate, and organic bases such as pyridine, triethylamine and lutidine. The amount of base is generally 1 to 3 moles and preferably 1 to 2 moles per mole of the compound represented by formula (XI).

Compounds represented by formula (XII) wherein W is -CO-O- include compounds represented by formula (XIV) with compounds represented by formula (VIIIa):

Can be produced by reacting in inert solvents such as chloroform, dichloromethane, dichloroethane, monochlorobenzene, acetone, methyl ethyl ketone, toluene, xylene, anisole, tetrahydrofuran, N, N-dimethylformamide and dimethyl sulfoxide have. The reaction temperature of the reaction is generally about −30 to 200 ° C. and preferably the boiling point of the inert solvent used to 150 ° C. The reaction is preferably carried out in the presence of an acid catalyst, and examples of acid catalysts include organic acids such as trifluoromethanesulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid and methanesulfonic acid, inorganic acids such as sulfuric acid and hydrochloric acid, and Nafion (registered). Strong acid sulfonic acid resins). The reaction is preferably carried out in the presence of polymerization inhibitors, such as phenolic polymerization inhibitors such as hydroquinone and hydroquinone monomethyl ether, to prevent the compound represented by the formula (XIV) from polymerizing during the reaction.

The amount of the compound represented by formula (VIIIa) is generally 0.5 to 5 mol and preferably 0.8 to 2 mol per mol of the compound represented by formula (XIV). The amount of acid catalyst is generally 0.001 to 3 mol and preferably 0.01 to 1 mol per mol of the compound represented by the formula (XIV). The amount of polymerization inhibitor is generally from 0.01 ppm to 0.1 mol and preferably from 1 ppm to 0.01 mol per mol of the compound represented by the formula (XIV).

The reaction of the compound represented by formula (VIIIa) and the compound represented by formula (XIV) is also preferably carried out in the presence of a dehydrating agent. The amount of dehydrating agent includes the same as described above, and the amount of dehydrating agent is generally 1 to 3 moles and preferably 1 to 2 moles per mole of the compound represented by the formula (XIV).

Oxime (I), in which n is 1, W is -CO-O-, and R ¹ is represented by the following formula:

Where R ⁵ and R ⁶ have the same meaning as defined above,

Compounds represented by the formula (XV) are:

Where Y, Z, Q ¹ and Q ² have the same meaning as defined above,

In the compound represented by the formula (XIV) and inert solvents such as toluene, tetrahydrofuran, dioxane, n-heptane, chloroform and dichloromethane, in the presence of a metal catalyst, from room temperature to 150 ° C, preferably from 50 to 100 ° C It may also be produced by reacting with stirring at temperature.

The amount of the compound represented by formula (XIV) is generally 0.9 to 5 mol and preferably 1 to 2 mol per mol of the compound represented by formula (XV). Examples of metal catalysts include titanium tetraisopropoxide and samarium triisopropoxide. The amount of metal catalyst is generally from 0.01 to 0.8 mol and preferably from 0.03 to 0.2 mol per mol of the compound represented by the formula (XV).

The resist composition of this invention contains resin and oxime (I).

Examples of the resin include resins which are insoluble or poorly soluble in aqueous alkali solution, but soluble in aqueous alkali solution by the action of an acid, and comprising a structural unit having an acid-labile group.

Oxime (I) acts as an acid generator.

As used herein, "acid-labile group" means a group that is removable by the action of an acid.

In the present specification, "-COOR" may be described as "structure with ester of carboxylic acid", and may be abbreviated as "ester group". Specifically, "-COOC (CH ₃ ) ₃ " may be described as "structure with tert-butyl ester of carboxylic acid" or may be abbreviated as "tert-butyl ester group".

Examples of acid-labile groups include alkyl ester groups in which the carbon atoms adjacent to oxygen atoms are quaternary carbon atoms, alicyclic ester groups in which carbon atoms adjacent to oxygen atoms are quaternary carbon atoms, and carbon atoms adjacent to oxygen atoms 4 Included are structures having esters of carboxylic acids such as lactone ester groups that are primary carbon atoms. "Quarter carbon atom" means "carbon atom joined to four substituents other than hydrogen atoms." Other examples of acid-labile groups include groups having three carbon atoms and a quaternary carbon atom bonded to one -OR ', where R' represents an alkyl group.

Examples of acid-labile groups include alkyl ester groups wherein the carbon atoms adjacent to the oxygen atoms are quaternary carbon atoms such as tert-butyl ester groups; Methoxymethyl ester, ethoxymethyl ester, 1-ethoxyethyl ester, 1-isobutoxyethyl ester, 1-isopropoxyethyl ester, 1-ethoxypropoxy ester, 1- (2-methoxyethoxy) Ethyl ester, 1- (2-acetoxyethoxy) ethyl ester, 1- [2- (1-adamantyloxy) ethoxy] ethyl ester, 1- [2- (1-adamantanecarbonyloxy) Acetal type ester groups such as ethoxy] ethyl ester, tetrahydro-2-furyl ester and tetrahydro-2-pyranyl ester group; Alicyclic ester groups where the carbon atoms adjacent to the oxygen atoms are quaternary carbon atoms, such as isobornyl esters, 1-alkylcycloalkyl esters, 2-alkyl-2-adamantyl esters and 1- (1-a) Mannyl) -1-alkylalkyl ester groups are included. At least one hydrogen atom of the adamantyl group may be substituted with a hydroxyl group.

Examples of structural units having acid-labile groups include structural units derived from esters of acrylic acid, structural units derived from esters of methacrylic acid, structural units derived from esters of norbornenecarboxylic acid, tricyclo Structural units derived from esters of decenecarboxylic acids and structural units derived from esters of tetracyclodecenecarboxylic acids. Preferred are structural units derived from esters of acrylic acid and from esters of methacrylic acid.

The resin used in the present composition can be obtained by carrying out a polymerization reaction of a monomer or monomers having an acid-labile group and an olefin double bond.

Among the monomers, bulky and acid- such as alicyclic ester groups (eg, 2-alkyl-2-adamantyl esters and 1- (1-adamantyl) -1-alkylalkyl ester groups) Monomers having labile groups are preferred because excellent resolution is obtained when the resulting resin is used in the present resist composition.

Examples of such monomers comprising macro and acid-labile groups include 2-alkyl-2-adamantyl acrylate, 2-alkyl-2-adamantyl methacrylate, 1- (1-adamantyl) -1 -Alkylalkyl acrylate, 1- (1-adamantyl) -1-alkylalkyl methacrylate, 2-alkyl-2-adamantyl 5-norbornene-2-carboxylate, 1- (1 -Adamantyl) -1-alkylalkyl 5-norbornene-2-carboxylate, 2-alkyl-2-adamantyl α-chloroacrylate and 1- (1-adamantyl) -1-alkyl Alkyl α-chloroacrylates are included.

In particular, 2-alkyl-2-adamantyl acrylate, 2-alkyl-2-adamantyl methacrylate or 2-alkyl-2-adamantyl α-chloroacrylate are monomers for the resin component in the present resist composition. When used as a resist composition, a resist composition having excellent resolution tends to be obtained. Typical examples thereof include 2-methyl-2-adamantyl acrylate, 2-methyl-2-adamantyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2-ethyl-2-adamant Methyl acrylate, 2-ethyl-2-adamantyl methacrylate, 2-n-butyl-2-adamantyl acrylate, 2-methyl-2-adamantyl α-chloroacrylate and 2-ethyl- 2-adamantyl α-chloroacrylate is included.

Especially 2-alkyl-2-adamantyl acrylate, 2-ethyl-2-adamantyl methacrylate, 2-isopropyl-2-adamantyl acrylate or 2-isopropyl-2-adamantyl meta When acrylates are used for the present resist composition, resist compositions with excellent sensitivity and heat resistance tend to be obtained. In the present invention, if necessary, two or more kinds of monomers having a group or groups which are dissociated by the action of an acid may be used together.

2-alkyl-2-adamantyl acrylate can generally be produced by reacting 2-alkyl-2-adamantanol or a metal salt thereof with an acrylic halide, and 2-alkyl 2-adamantyl methacrylate can generally be produced by reacting 2-alkyl-2-adamantanol or a metal salt thereof with methacrylic halide.

The resin may also include structural units represented by formula (Xa) as structural units having acid-labile groups:

Wherein R ^1a represents a hydrogen atom, a halogen atom, a C1-C4 alkyl group or a C1-C4 perfluoroalkyl group, Z ^a represents ^a single bond or-[CH ₂ ] _a -CO-X ^4a- , X ^1a , X ^2a , X ^3a and X ^4a each independently represent —O— or —S—, a represents an integer of 1 to 4, l represents an integer of 1 to 3, and m represents an integer of 0 to 3 Indicates.

Examples of halogen atoms include fluorine atoms and chlorine atoms. Examples of C1-C4 alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and tert-butyl group. Examples of C1-C4 perfluoroalkyl group include trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group and nonafluorobutyl group.

Examples of monomers used to obtain the structural unit represented by formula (Xa) include the following:

Such monomers can be produced by reacting a corresponding alcohol compound with acryloyl chloride or methacryloyl chloride in the presence of a base.

Resins used in the present resist composition may also include other structural units or units derived from acid-stable monomers in addition to the above structural units having acid-labile groups. Here, "structural unit derived from an acid-stable monomer" means "structural unit not dissociated by acid".

Examples of such other structural units derived from acid-stable monomers include structural units derived from monomers having free carboxyl groups such as acrylic acid and methacrylic acid; Structural units derived from aliphatic unsaturated dicarboxylic anhydrides such as maleic anhydride and itaconic anhydride; Structural units derived from 2-norbornene; Structural units derived from acrylonitrile or methacrylonitrile; Structural units derived from alkyl acrylates or alkyl methacrylates wherein the carbon atom adjacent to the oxygen atom is a secondary or 3-second carbon atom; Structural units derived from 1-adamantyl acrylate or 1-adamantyl methacrylate; structural units derived from styrene monomers such as p-hydroxystyrene and m-hydroxystyrene; Structural units derived from methacryloyloxy-γ-butyrolactone or acryloyloxy-γ-butyrolactone having a lactone ring which may be substituted with an alkyl group; Etc. are included. Wherein the 1-adamantyloxycarbonyl group is an acid-stable group, even if the carbon atom adjacent to the oxygen atom is a quaternary carbon atom, and the 1-adamantyloxycarbonyl group may be substituted with at least one hydroxyl group have.

Specific examples of structural units derived from acid-stable monomers include structural units derived from 3-hydroxy-1-adamantyl acrylate;

Structural units derived from 3-hydroxy-1-adamantyl methacrylate;

Structural units derived from 3,5-dihydroxy-1-adamantyl acrylate;

Structural units derived from 3,5-dihydroxy-1-adamantyl methacrylate;

structural units derived from α-acryloyloxy-γ-butyrolactone;

structural units derived from α-methacryloyloxy-γ-butyrolactone;

structural units derived from β-acryloyloxy-γ-butyrolactone;

structural units derived from β-methacryloyloxy-γ-butyrolactone;

The structural unit represented by formula (k1):

Wherein R ²¹ represents a hydrogen atom or a methyl group, R ²³ is independently a methyl group, a trifluoromethyl group or a halogen atom in each occurrence, and p represents an integer of 0 to 3;

The structural unit represented by formula (k2):

Wherein R ²² represents a hydrogen atom or a methyl group, R ²⁴ independently represents a methyl group, a trifluoromethyl group or a halogen atom at each occurrence, and q represents an integer of 0 to 3;

structural units derived from p-hydroxystyrene;

structural units derived from m-hydroxystyrene;

Structural units derived from an alicyclic compound having an olefinic double bond, such as the structural unit represented by formula (k3):

Wherein R ²⁵ and R ²⁶ each independently represent a hydrogen atom, a C1-C3 alkyl group, a C1-C3 hydroxylalkyl group, a carboxyl group, a cyano group, a hydroxyl group or a -COOU group, where U represents an alcohol moiety, or Or R ²⁵ and R ²⁶ can be joined together to form an anhydrous carboxylic acid residue represented by -C (= 0) OC (= 0)-;

Structural units derived from aliphatic unsaturated anhydride dicarboxylic acids, such as the structural units represented by formula (k4):

;

;

The structural unit shown by Formula (5), etc. are contained.

In particular, structural units derived from p-hydroxystyrene, structural units derived from m-hydroxystyrene, structures derived from 3-hydroxy-1-adamantyl acrylate in addition to the structural units having acid-labile groups Unit, structural unit derived from 3-hydroxy-1-adamantyl methacrylate, structural unit derived from 3,5-dihydroxy-1-adamantyl acrylate, 3,5-dihydroxy- A resin further having at least one structural unit selected from the group consisting of a structural unit derived from 1-adamantyl methacrylate, a structural unit represented by formula (k1) and a structural unit represented by formula (k2), is provided on the substrate It is preferable in view of the adhesion of the resist to the resist and the resolution of the resist.

3-hydroxy-1-adamantyl acrylate, 3-hydroxy-1-adamantyl methacrylate, 3,5-dihydroxy-1-adamantyl acrylate and 3,5-dihydroxy -1-adamantyl methacrylate can be produced, for example, by reacting the corresponding hydroxyadamantane with acrylic acid, methacrylic acid or acid halides thereof, and these are also commercially available. .

In addition, acryloyloxy- [gamma] -butyrolactone and methacryloyloxy- [gamma] -butyrolactone can react the corresponding [alpha]-or [beta] -bromo- [gamma] -butyrolactone with acrylic acid or methacrylic acid or Or by reacting the corresponding α- or β-hydroxy-γ-butyrolactone with an acrylic halide or methacrylic halide.

Examples of the monomer for obtaining the structural units represented by the formulas (k1) and (k2) include methacrylates of cycloaliphatic lactones having the following hydroxyl groups, acrylates of cycloaliphatic lactones, and mixtures thereof. Such esters can be produced, for example, by reacting the corresponding alicyclic lactones having hydroxyl groups with acrylic acid or methacrylic acid, and methods for their preparation are described, for example, in JP 2000-26446 A.

Examples of acryloyloxy-γ-butyrolactone and methacryloyloxy-γ-butyrolactone in which the lactone ring may be substituted with an alkyl group include

α-acryloyloxy-γ-butyrolactone,

α-methacryloyloxy-γ-butyrolactone,

α-acryloyloxy-β, β-dimethyl-γ-butyrolactone,

α-methacryloyloxy-β, β-dimethyl-γ-butyrolactone,

α-acryloyloxy-α-methyl-γ-butyrolactone,

α-methacryloyloxy-α-methyl-γ-butyrolactone,

β-acryloyloxy-γ-butyrolactone,

β-methacryloyloxy-γ-butyrolactone and

β-methacryloyloxy-α-methyl-γ-butyrolactone is included.

Resin comprising a structural unit derived from 2-norbornene shows a strong structure because the alicyclic group is present directly on its main chain, and exhibits excellent dry etching resistance. Structural units derived from 2-norbornene are, for example, subjected to radical polymerization using aliphatic unsaturated dicarboxylic acids such as maleic anhydride and itaconic anhydride in addition to the corresponding 2-norbornene. It can be introduced into the main chain. The structural unit derived from 2-norbornene is formed by the opening of its double bond and can be represented by the above formula (k3). Structural units derived from maleic anhydride and from itaconic anhydride, which are structural units derived from aliphatic unsaturated dicarboxylic acids, are formed by the opening of their double bonds, and the above formulas (k4) and (k5) Each can be represented by

In R ²⁵ and R ²⁶ , examples of C 1 -C 3 alkyl groups include methyl, ethyl, and n-propyl groups, and examples of C 1 -C 3 hydroxyalkyl groups include hydroxymethyl and 2-hydroxyethyl groups.

In R ²⁵ and R ²⁶ , the -COOU group is an ester formed from a carboxyl group, and examples of the alcohol residue corresponding to U include optionally substituted C 1 -C 8 alkyl groups, 2-oxooxolane-3-yl groups and 2-oxooxolane 4-yl groups are included, and examples of substituents on C1-C8 alkyl groups include hydroxyl groups and cycloaliphatic hydrocarbons.

Specific examples of the monomer used to obtain the structural unit represented by the formula (k3) described above include 2-norbornene, 2-hydroxy-5-norbornene, 5-norbornene-2-carboxylic acid, methyl 5-norbornene-2-carboxylate, 2-hydroxyethyl 5-norbornene-2-carboxylate, 5-norbornene-2-methanol and 5-norbornene-2,3- anhydrous Dicarboxylic acids may be included.

When U in the —COOU group is an acid-labile group, the structural unit represented by formula (k3) is a structural unit having an acid-labile group, even though it has a norbornane structure. Examples of the monomer for obtaining the structural unit having an acid-labile group include tert-butyl 5-norbornene-2-carboxylate and 1-cyclohexyl-1-methylethyl 5-norbornene-2-carboxylate , 1-methylcyclohexyl 5-norbornene-2-carboxylate, 2-methyl-2-adamantyl 5-norbornene-2-carboxylate, 2-ethyl-2-adamantyl 5-norbornene-2-carboxylate, 1- (4-methylcyclohexyl) -1-methylethyl 5-norbornene-2-carboxylate, 1- (4-hydroxycyclohexyl) -1 -Methylethyl 5-norbornene-2-carboxylate, 1-methyl-1- (4-oxocyclohexyl) ethyl 5-norbornene-2-carboxylate and 1- (1-adamantyl) -1-methylethyl-5-norbornene-2-carboxylate is included.

The resin may comprise a structural unit represented by formula (b1), or a structural unit having one or more fluorine atoms:

Wherein R ²⁷ is a hydrogen atom, a methyl group or a trifluoromethyl group, and AR is a C1-C30 fluorine-containing linear, branched chain or cyclic hydrocarbon group, which may comprise one or more hydroxyl groups and wherein At least one methylene group may be replaced with —O—, —S— or —N (R ^c ) —, and R ^c has the same meaning as described above.

Examples of the monomer which obtains the structural unit represented by formula (b1) include the followings:

The resin used in the composition is preferably a structural unit having an acid-labile group generally in the total structural units of the resin, although the ratio varies depending on the type of radiation for patterning exposure, the type of acid-labile group, and the like. 10 to 80 mol%.

Especially 2-alkyl-2-adamantyl acrylate, 2-alkyl-2-adamantyl methacrylate, 1- (1-adamantyl) -1-alkylalkyl acrilate or 1- (1 When a structural unit derived from -adamantyl) -1-alkylalkyl methacrylate is used as a structural unit having an acid-labile group, it is preferable that the proportion of the structural unit is 15 mol% or more in the total structural units of the resin. -Favorable etching resistance

The resin may have a structural unit derived from an oxime compound represented by formula (Va).

Resins used in the present invention can generally be produced by carrying out the polymerization of the corresponding monomer or monomers. The resin can also be produced by polymerizing the oligomer obtained after carrying out the oligomerization reaction of the corresponding monomer or monomers.

The polymerization reaction is generally carried out in the presence of a radical initiator.

Radical initiators are not limited, and examples thereof include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane- 1-carbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl-2 Azo compounds such as 2'-azobis (2-methylpropionate) and 2,2'-azobis (2-hydroxymethylpropionitrile); Lauroyl peroxide, tert-butyl hydroperoxide, benzoyl peroxide, tert-butyl peroxybenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl Organic hydroperoxides such as peroxydicarbonate, tert-butyl peroxyneodecanoate, tert-butyl peroxypivalate and 3,5,5-trimethylhexanoyl peroxide; And inorganic peroxides such as potassium peroxodisulfate, ammonium peroxodisulfate and hydrogen peroxide. Among these, azo compounds are preferable, and 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1- More preferred are carbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile) and dimethyl-2,2'-azobis (2-methylpropionate).

Such radical initiators may be used alone or in the form of mixtures of two or more thereof. When a mixture of two or more thereof is used, the mixing ratio is not limited.

The amount of radical initiator is preferably 1 to 20 mol% based on the molar amount of all monomers or oligomers.

The polymerization temperature is generally 0 to 150 ° C, and preferably 40 to 100 ° C.

The polymerization reaction is generally carried out in the presence of a solvent, and it is preferable to use a solvent sufficient to dissolve the monomer, the radical initiator and the obtained resin. Examples thereof include hydrocarbon solvents such as toluene; Ether solvents such as 1,4-dioxane and tetrahydrofuran; Ketone solvents such as methyl isobutyl ketone; Alcohol solvents such as isopropyl alcohol; cyclic ester solvents such as γ-butyrolactone; Glycol ether ester ester solvents such as propylene glycol monomethyl ether acetate; And acyclic ester solvents such as ethyl lactate. Such solvents may be used alone and mixtures thereof may be used.

The amount of solvent is not limited and substantially, it is preferably 1 to 5 parts by weight based on 1 part of all monomers or oligomers.

When alicyclic compounds having olefinic double bonds and aliphatic unsaturated anhydrous dicarboxylic acids are used as monomers, it is preferable to use them in excess in view of the tendency that they are not easily polymerized.

After completion of the polymerization reaction, the resin produced can be separated, for example, by adding a solvent in which the resin present is insoluble or poorly soluble to the obtained reaction mixture and filtering the precipitated resin. If desired, the separated resin can be purified, for example, by washing with a suitable solvent.

The polymers of the present invention comprise structural units derived from oxime compounds represented by formula (Va), which are novel polymers.

The polymer may consist of structural units derived from an oxime compound represented by formula (Va) and may comprise other structural units or units in addition to the structural unit derived from an oxime compound represented by formula Va.

Examples of other structural units include structural units having acid-labile groups, structural units having acid-labile groups. Examples of the structural unit having an acid-labile group and the structural unit having an acid-labile group include the same as those described above.

When the polymer of the present invention comprises a structural unit having an acid-labile group, the proportion of the structural unit having an acid-labile group is generally 5 to 95 mol% and preferably 30 to 90 mol% of the total structural units of the polymer. to be.

When the polymer comprises structural units having acid-stable groups, the proportion of structural units having acid-stable groups is generally from 5 to 95 mol%, preferably from 30 to 60 mol% and more preferably in the total structural units of the resin. Preferably from 40 to 50 mol%.

The polymer of the present invention can be prepared by polymerizing an oxime compound represented by formula (Va) or by polymerizing an oxime compound represented by formula (Va) and other monomers or monomers.

The resist composition of the present invention may comprise the polymer of the present invention and may comprise the above-described resin and the polymer of the present invention. This polymerization reaction can be carried out according to the polymerization reaction described above.

As mentioned above, oxime (I) acts as an acid generator.

The resist composition of the present invention also includes other acid generator (s).

An acid generator is a substance that decomposes to generate an acid by applying radiation such as light, an electron beam, or the like on the material itself or on a resist composition comprising the material. The acid generated from the acid generator acts on the resin and / or the present polymer to cleave the acid-labile groups present in the resin and / or the present polymer.

Examples of acid generators include onium salt compounds, organo-halogen compounds, sulfone compounds and sulfonate compounds. Onium salt compounds are preferred.

The acid generator described in JP 2003-5374 A1 may be used in the present resist composition.

Examples of onium salt compounds include diphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenylyodonium hexafluoroantimonate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate , Bis (4-tert-butylphenyl) iodonium tetrafluoroborate, bis (4-tert-butylphenyl) iodonium hexafluorophosphate, bis (4-tert-butylphenyl) iodonium hexafluoro Antimonate, bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium trifluoro Methanesulfonate, triphenylsulfonium adamantylmethoxycarbonyldifluoromethanesulfonate, triphenylsulfonium (3-hydroxyadamantyl) methoxycarbonyldifluoromethanesulfonate, triphenylsulfonium 1 -(3-high Roxymethyladamantyl) methoxycarbonyldifluoromethanesulfonate, triphenylsulfonium 1- (hexahydro-2-oxo-3,5-methano-2H-cyclopenta [b] furan-6-yljade Cycarbonyl) difluoromethanesulfonate, triphenylsulfonium 4-oxo-1-adamantyloxycarbonyldifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfonium hexafluoroantimonate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, p-tolyldiphenylsulfonium trifluoromethanesulfonate, p-tolyldiphenylsulfonium heptadecafluorooctanesulfonate, 2,4,6 -Trimethylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-tert-butylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-phenylthiophenyldiphenylsulfonium hexafluorophosphate, 4-phenylthio Phenyldiphenylsulfonium hexafluoroantimonate, 1- (2-naphthoylmethyl) thiolanium hexaple Oroantimonate (1- (2-naphthoylmethyl) thiolanium hexafluoroantimonate), 1- (2-naphthoylmethyl) thiolanium trifluoromethanesulfonate, 4-hydroxy-1-naphthyldimethylsulfonium hexafluoro Antimonates and 4-hydroxy-1-naphthyldimethylsulfonium trifluoromethanesulfonate.

Examples of organic halide compounds include

2-methyl-4,6-bis (trichloromethyl) -1,3,5-triazine,

2,4,6-tris (trichloromethyl) -1,3,5-triazine,

2-phenyl-4,6-bis (trichloromethyl) -1,3,5-triazine,

2- (4-chlorophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine,

2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine,

2- (4-methoxy-1-naphthyl) -4,6-bis (trichloromethyl) -1,3,5-triazine,

2- (benzo [d] [1,3] dioxolan-5-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine,

2- (4-methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine,

2- (3,4,5-trimethoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine,

2- (3,4-dimethoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine,

2- (2,4-dimethoxystyryl) -4,6-bis (trichloromethyl) -1,3-triazine,

2- (2-methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine,

2- (4-butoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine and

2- (4-pentyloxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine are included.

Examples of sulfone compounds include diphenyl disulfone, di-p-tolyl disulfone, bis (phenylsulfonyl) diazomethane, bis (4-chlorophenylsulfonyl) diazomethane, bis (p-tolylsulfonyl) dia Crude methane, bis (4-tert-butylphenylsulfonyl) diazomethane, bis (2,4-xylylsulfonyl) diazomethane (bis (2,4-xylylsulfonyl) diazomethane), bis (cyclohexylsul Ponyl) diazomethane, (benzoyl) (phenylsulfonyl) diazomethane, N- (phenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoro Chloromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) -5-norbornene-2,3-dicarbodiimide, N- (trifluoromethylsulfonyloxy) naphthal Imides and N- (10-camphorsulfonyloxy) naphthalimide.

Examples of the sulfonate compound include 1-benzoyl-1-phenylmethyl p-toluenesulfonate, 2-benzoyl-2-hydroxy-2-phenylethyl o-toluenesulfonate, 1,2,3-benzenetriyl trismethane Sulfonates, 2,6-dinitrobenzyl p-toluenesulfonate, 2-nitrobenzyl p-toluenesulfonate and 4-nitrobenzyl p-toluenesulfonate.

The resist composition preferably comprises 0.1 to 50% by weight of other acid generators based on the amount of the resin component.

The polymer acts as an acid generator.

The resist composition preferably comprises 80 to 99.9% by weight of the resin component and 0.1 to 20% by weight of the acid generator component based on the sum of the resin component and the acid generator component. Here, "acid generator component" means the present polymer, other acid generator (s) or mixtures thereof comprising structural units derived from an oxime compound represented by oxime (I), formula (Va).

When the resist composition comprises oxime (I) and other acid generator (s), it is generally 0.01 / 99.99 to 99.99 / 0.01, although the ratio of the present polymer and other acid generator (s) is not limited. .

When the resist composition comprises the present polymer and other acid generator (s) comprising structural units derived from the oxime compound represented by formula (Va), the proportion of the present polymer and other acid generator (s) is not limited. If not, this is generally between 0.01 / 99.99 and 99.99 / 0.01.

The resist composition may comprise oxime (I) and the present polymer, and the proportion of the present polymer and other acid generator (s) is not limited.

In the present resist composition, performance deterioration due to inactivation of the acid resulting from post exposure delay results in the addition of organic base compounds, in particular nitrogen-containing organic base compounds, as quencher. Can be reduced.

Specific examples of nitrogen-containing organic base compounds include amine compounds represented by the following formula:

Wherein R ¹¹ and R ¹² independently represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and the alkyl, cycloalkyl and aryl groups are amino groups which may be substituted with hydroxyl groups, C 1 -C 4 alkyl groups, and C 1 -C 6 alkoxy May be substituted with at least one group selected from C1-C6 alkoxy groups which may be substituted with groups,

R ¹³ and R ¹⁴ independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an alkoxy group, and the alkyl, cycloalkyl, aryl and alkoxy groups are amino groups which may be substituted with hydroxyl groups, C1-C4 alkyl groups, and C1 May be substituted with at least one selected from a -C6 alkoxy group, or R ¹³ and R ¹⁴ may be bonded together with the carbon atoms to which they combine to form an aromatic ring,

R ¹⁵ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group or a nitro group, and the alkyl, cycloalkyl, aryl and alkoxy groups are amino groups which may be substituted with hydroxyl groups, C1-C4 alkyl groups, and C1-C6 May be substituted with at least one group selected from an alkoxy group,

R ¹⁶ represents an alkyl or cycloalkyl group, and the alkyl and cycloalkyl group may be substituted with at least one group selected from a hydroxyl group, an amino group which may be substituted with a C1-C4 alkyl group, and a C1-C6 alkoxy group,

And

W ¹ is —CO—, —NH—, —S—, —SS—, an alkylene group in which at least one methylene group may be replaced by —O—, or an alke in which at least one methylene group may be replaced by —O— Represents a niylene group,

And quaternary ammonium hydroxides represented by the following formula:

Wherein R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are independently an alkyl group, a cycloalkyl group or an aryl group, and the alkyl, cycloalkyl and aryl groups are an amino group which may be substituted with a hydroxyl group, a C1-C4 alkyl group, and C1 It may be substituted with at least one group selected from -C6 alkoxy group.

The alkyl group in R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ is preferably about 1 to 10 carbon atoms, and more preferably about 1 To 6 carbon atoms.

Examples of amino groups that may be substituted with C 1 -C 4 alkyl groups include amino, methylamino, ethylamino, n-butylamino, dimethylamino and diethylamino groups. Examples of C1-C6 alkoxy groups which may be substituted with C1-C6 alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, n-pentyloxy, n -Hexyloxy and 2-methoxyethoxy groups.

Specific examples of the alkyl group which may be substituted with at least one selected from a hydroxyl group, an amino group which may be substituted with a C1-C4 alkyl group, and a C1-C6 alkoxy group which may be substituted with a C1-C6 alkoxy group include methyl, ethyl, n -Propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, 2- (2-methoxyethoxy) ethyl, 2-high Hydroxyethyl, 2-hydroxypropyl, 2-aminoethyl, 4-aminobutyl and 6-aminohexyl groups.

The cycloalkyl group in R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ preferably has about 5 to 10 carbon atoms. Specific examples of the cycloalkyl group which may be substituted with at least one group selected from a hydroxyl group, a C1-C4 alkyl group, and a C1-C6 alkoxy group include cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl groups do.

The aryl groups in R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ preferably have about 6 to 10 carbon atoms. Specific examples of the aryl group which may be substituted with at least one group selected from a hydroxyl group, a C1-C4 alkyl group, and a C1-C6 alkoxy group include phenyl and naphthyl groups.

The alkoxy group in R ¹³ , R ¹⁴ and R ¹⁵ preferably has about 1 to 6 carbon atoms and specific examples thereof include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tertiary Butoxy, n-pentyloxy and n-hexyloxy groups are included.

The alkylene and alkenylene groups in W preferably have 2 to 6 carbon atoms. Specific examples of the alkylene group include ethylene, trimethylene, tetramethylene, methylenedioxy and ethylene-1,2-dioxy groups, and specific examples of alkenylene groups include ethene-1,2-diyl, 1-propene -1,3-diyl and 2-butene-1,4-diyl groups are included.

Specific examples of the amine compound include n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, aniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4 -Nitroaniline, 1-naphthylamine, 2-naphthylamine, ethylenediamine, tetramethylenediamine, hexamethylene diamine, 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino -3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, Dinonylamine, didecylamine, N-methylaniline, piperidine, diphenylamine, triethylamine, trimethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctyl Amine, trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine, methyldihexylamine, methyldicyclohexylamine, methyldiheptylamine, methyldioctylamine, methyldino Amine, methyldidecylamine, ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldioctylamine, ethyldinonylamine, ethyldidecylamine, dicyclohexylmethylamine, tris [ 2- (2-methoxyethoxy) ethyl] amine, triisopropanolamine, N, N-dimethylaniline, 2,6-diisopropylaniline, imidazole, benzimidazole, pyridine, 4-methylpyridine, 4- Methylimidazole, bipyridine, 2,2'-dipyridylamine, di-2-pyridyl ketone, 1,2-di (2-pyridyl) ethane, 1,2-di (4-pyridyl) Ethane, 1,3-di (4-pyridyl) propane, 1,2-bis (2-pyridyl) ethylene, 1,2-bis (4-pyridyl) ethylene, 1,2-bis (4-pyri Diloxy) ethane, 4,4'-dipyridyl sulfide, 4,4'-dipyridyl disulfide, 1,2-bis (4-pyridyl) ethylene, 2,2'-dipicolylamine (2 , 2'-dipicolylamine) and 3,3'-dipicolylamine.

Examples of quaternary ammonium hydroxides include tetramethylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, phenyltrimethylammonium hydroxide, (3-trifluoro Romethylphenyl) trimethylammonium hydroxide and (2-hydroxyethyl) trimethylammonium hydroxide (ie “choline”).

Hindered amine compounds having a piperidine backbone as disclosed in JP 11-52575 A1 can also be used as quencher.

In view of forming a pattern with higher resolution, quaternary ammonium hydroxides are preferably used as quencher.

When the basic compound is used as the quencher, the present resist composition preferably contains 0.01 to 1% by weight of the basic compound based on the total amount of the resin component and the acid generator component.

The resist composition may contain small amounts of various additives such as photosensitizers, dissolution inhibitors, other polymers, surfactants, stabilizers and dyes, if necessary, so long as the effects of the present invention are not prevented.

The resist composition is generally in the form of a resist liquid composition in which the components are dissolved in a solvent, and the resist liquid composition is applied on a substrate such as a silicon wafer by conventional methods such as spin coating. The solvent used is sufficient to dissolve the above-mentioned components, have a suitable drying rate, and provide a uniform and smooth coating after evaporation of the solvent. Solvents commonly used in this technique can be used.

Examples of the solvent include glycol ether esters such as ethyl cellosolve acetate, methyl cellosolve acetate and propylene glycol monomethyl ether acetate; Acyclic esters such as ethyl lactate, butyl acetate, amyl acetate and ethyl pyruvate; Ketones such as acetone, methyl isobutyl ketone, 2-heptanone and cyclohexane; And cyclic esters such as γ-butyrolactone. These solvents may be used alone and two or more thereof may be used in combination.

The resist film applied on the substrate and then dried is exposed for patterning, then heat-treated to facilitate the deblocking reaction, and then developed with an alkali developer. The alkali developer used may be any one of the various alkaline aqueous solutions used in the art. In general, aqueous solutions of tetramethylammonium hydroxide or (2-hydroxyethyl) trimethylammonium hydroxide (commonly known as "choline") are often used.

Example

The invention will be explained in more detail by way of examples, which are not to be construed as limiting the scope of the invention.

The "%" and "part (s)" used to indicate the amount of a substance and the amount of a substance used in the Examples and Comparative Examples below are based on weight unless specifically stated otherwise. The weight-average molecular weight of any of the materials used in the examples below was determined by gel permeation chromatography [HLC-8120GPC type, column (three columns) using styrene as standard reference material. : TSKgel Multopore HXL-M, Solvent: Tetrahydrofuran, manufactured by TOSOH CORPORATION. The structure of the compound is NMR (GX-270 type or EX-270 type, manufactured by JEOL LTD.) And mass spectrometry (liquid chromatography: 1100 type, manufactured by AGILENT TECHNOLOGIES LTD., Mass spectrometry). : LC / MSD type or LC / MSD TOF type, manufactured by Agilent Technologies Inc.).

Example 1

To a solution prepared by dissolving 5.0 parts of trifluoroacetophenone oxime in 6.6 parts of N, N-dimethylformamide, 3.0 parts of 2,6-lutidine and 9.9 parts of the compound represented by the formula (a) were added. The resulting mixture was stirred for 16 hours at room temperature. To the obtained reaction mixture, saturated aqueous ammonium chloride solution was added, and then the obtained mixture was extracted with ethyl acetate. The organic layer obtained was washed with ion-exchanged water and then concentrated under reduced pressure. The obtained residue was purified by silica gel chromatography to obtain 8.7 parts of the compound represented by the formula (b), which is referred to as B1.

Example 2

To a solution prepared by dissolving 3.0 parts of trifluoroacetophenone oxime in 4.0 parts of N, N-dimethylformamide, 1.8 parts of 2,6-lutidine and 6.6 parts of the compound represented by the formula (c) were added. The resulting mixture was stirred for 16 hours at room temperature. To the obtained reaction mixture, saturated aqueous ammonium chloride solution was added, and then the obtained mixture was extracted with ethyl acetate. The organic layer obtained was washed with ion-exchanged water and then concentrated under reduced pressure. The obtained residue was purified by silica gel chromatography to obtain 5.0 parts of the compound represented by the formula (d), which is referred to as B2.

Example 3

To a solution prepared by dissolving 2.0 parts of trifluoroacetophenone oxime in 3.0 parts of N, N-dimethylformamide, 0.9 parts of 2,6-lutidine and 2.0 parts of the compound represented by the formula (e) were added. The resulting mixture was stirred for 17 hours at room temperature. To the obtained reaction mixture, saturated aqueous ammonium chloride solution was added, and then the obtained mixture was extracted with ethyl acetate. The organic layer obtained was washed with ion-exchanged water and then concentrated under reduced pressure. The obtained residue was purified by silica gel chromatography to obtain 1.9 parts of the compound represented by the formula (f), which is referred to as B3.

Example 4

To a solution prepared by dissolving 2.0 parts of trifluoroacetophenone oxime in 3.0 parts of N, N-dimethylformamide, 0.9 parts of 2,6-lutidine and 1.6 parts of the compound represented by the formula (g) were added. The resulting mixture was stirred for 17 hours at room temperature. To the obtained reaction mixture, saturated aqueous ammonium chloride solution was added, and then the obtained mixture was extracted with ethyl acetate. The organic layer obtained was washed with ion-exchanged water and then concentrated under reduced pressure. The obtained residue was purified by silica gel chromatography to obtain 1.2 parts of the compound represented by the formula (h), which is called B4.

Example 5

To the solution prepared by dissolving 1.0 part trifluoroacetophenone oxime in 0.9 part N, N-dimethylformamide, 0.7 parts 2,6-lutidine and 4.6 parts of the compound represented by the formula (i) were added. The resulting mixture was stirred at rt for 18 h. The reaction mixture obtained was purified by silica gel chromatography to obtain 1.7 parts of the compound represented by the formula (j), which is referred to as B5.

Example 6

To 1 part methanol, 0.5 part of the compound represented by the above formula (j) was added to prepare a solution. 0.01 part of p-toluenesulfonic acid monohydrate was added to the obtained solution. The resulting mixture was stirred for 6 hours at room temperature. The resulting reaction mixture was mixed with 10 parts methanol and 10 parts heptane. The methanol layer was obtained by separation. To the methanol layer, 3 parts of ion-exchanged water were added and then extracted with ethyl acetate. The organic layer obtained was washed and then concentrated under reduced pressure to yield 0.3 part of the compound represented by the formula (k), which is referred to as B6.

Example 7

To a solution prepared by dissolving 0.3 parts of the compound represented by the formula (k) in 2.3 parts of tetrahydrofuran, 0.2 parts of 2,6-lutidine and 0.2 parts of methacryloyl chloride were added. The resulting mixture was stirred at 0 ° C. for 1 hour. The reaction mixture obtained was purified by silica gel chromatography to obtain 0.3 part of the compound represented by the formula (l), which is called B7.

Example 8

(1) 4.4 parts 2-hydroxyethyl methacrylate, 0.05 parts sulfuric acid and 0.01 parts p-methoxyphenol to a solution prepared by mixing 5 parts difluoro (fluorosulfonyl) acetic acid and 66 parts dichloroethane. Was added and the resulting mixture was stirred at reflux for 1 h. The reaction mixture obtained was cooled to room temperature and 80 parts of ion-exchanged water was added thereto and then extracted with 200 parts of chloroform. The organic layer obtained is washed three times with water and then concentrated under reduced pressure to give 8.4 parts of the compound represented by the formula (m) above.

(2) To a solution prepared by dissolving 1.5 parts of trifluoroacetophenone oxime in 2.5 parts of N, N-dimethylformamide, 0.9 parts of 2,6-lutidine and 3.1 parts of the compound represented by the formula (m) are added. It was. The resulting mixture was stirred at rt for 18 h. To the obtained reaction mixture, saturated aqueous ammonium chloride solution was added, and then the obtained mixture was extracted with ethyl acetate. The organic layer obtained was washed with ion-exchanged water and then concentrated under reduced pressure. The obtained residue was purified by silica gel chromatography to obtain 3.0 parts of the compound represented by the formula (n), which is called B8.

Example 9

To a solution prepared by mixing 10 parts of the compound represented by the formula (h) and 50 parts of chloroform, 3.5 parts of 2-hydroxyethyl methacrylate, 0.01 parts of p-methoxyphenol and 0.76 parts of titanium tetraisopropoxide were added. Added. The resulting mixture was stirred at reflux for 40 h. The reaction mixture obtained was cooled to room temperature and 6 parts of silica gel was added thereto. The resulting mixture was stirred for 30 minutes and then filtered. The filtrate obtained was concentrated under reduced pressure. To the obtained residue, extraction was performed by adding n-heptane and ion-exchanged water. The organic layer obtained was washed three times with ion-exchanged water and then concentrated under reduced pressure to give 8.6 parts of the compound represented by the formula (n).

Example 10

To a solution prepared by mixing 30 parts of the compound represented by the formula (h) and 150 parts of chloroform, 12.15 parts of 2-hydroxyethyl methacrylate, 0.04 parts of p-methoxyphenol and 1.27 parts of samarium triisopropoxide Was added. The resulting mixture was stirred at reflux for 23 h. The resulting reaction mixture was cooled to room temperature and 12 parts of silica gel was added thereto. The resulting mixture was stirred for 30 minutes and then filtered. The filtrate obtained was concentrated under reduced pressure. To the obtained residue, extraction was performed by adding n-heptane and ion-exchanged water. The organic layer obtained was washed three times with ion-exchanged water and then concentrated under reduced pressure to give 25.5 parts of the compound represented by the formula (n).

Example 11

(1) To a solution prepared by mixing 5.27 parts of methyl difluoro (fluorosulfonyl) acetate and 25 parts of dichloroethane, 5.0 parts of 3-hydroxyadamantanemethanol and 0.34 parts of titanium tetraisopropoxide are added. And the resulting mixture was stirred at reflux for 5 hours. The reaction mixture obtained was cooled to room temperature and 80 parts of ion-exchanged water was added thereto and then extracted with 200 parts of chloroform. The obtained organic layer was washed three times with water and then concentrated under reduced pressure to obtain 7.8 parts of the compound represented by the formula (o).

(2) To a solution prepared by dissolving 1.5 parts of trifluoroacetophenone oxime in 2.5 parts of N, N-dimethylformamide, 1.18 parts of 2,6-lutidine and 3.64 parts of the compound represented by the formula (o) are added. It was. The resulting mixture was stirred for 10 hours at room temperature. To the obtained reaction mixture, saturated aqueous ammonium chloride solution was added, and then the obtained mixture was extracted with ethyl acetate. The organic layer obtained was washed with ion-exchanged water and then concentrated under reduced pressure. The obtained residue was purified by silica gel chromatography to obtain 5.2 parts of the compound represented by the formula (p), which is referred to as B9.

Example 12

To a solution prepared by dissolving 2.0 parts of 1- (p-tolyl) heptafluorobutane oxime in 2.5 parts of N, N-dimethylformamide, 0.8 parts of 2,6-lutidine and 2.5 parts of the formula (a) Compound was added. The resulting mixture was stirred for 10 hours at room temperature. To the obtained reaction mixture, saturated aqueous ammonium chloride solution was added, and then the obtained mixture was extracted with ethyl acetate. The organic layer obtained was washed with ion-exchanged water and then concentrated under reduced pressure. The obtained residue was purified by silica gel chromatography to obtain 1.3 parts of the compound represented by the formula (q), which is called B10.

Example 13

(1) 5.0 parts of 3- (hydroxymethyl) adamantanemethanol and 0.34 parts of titanium tetraisopropoxide in a solution prepared by mixing 5.27 parts of methyl difluoro (fluorosulfonyl) acetate and 25 parts of dichloroethane. The side was added and the resulting mixture was stirred at reflux for 5 hours. The reaction mixture obtained was cooled to room temperature and 80 parts of ion-exchanged water was added thereto and then extracted with 200 parts of chloroform. The obtained organic layer was washed three times with water and then concentrated under reduced pressure to obtain 7.8 parts of the compound represented by the formula (r).

(2) To a solution prepared by dissolving 1.5 parts of trifluoroacetophenone oxime in 2.5 parts of N, N-dimethylformamide, 1.18 parts of 2,6-lutidine and 3.64 parts of the compound represented by the formula (r) were added. It was. The resulting mixture was stirred for 10 hours at room temperature. To the obtained reaction mixture, saturated aqueous ammonium chloride solution was added, and then the obtained mixture was extracted with ethyl acetate. The organic layer obtained was washed with ion-exchanged water and then concentrated under reduced pressure. The obtained residue was purified by silica gel chromatography to obtain 5.2 parts of the compound represented by the formula (s), which is referred to as B11.

Example 14

(1) 3.9 parts of 3,3,4,4,5,5,6,6,6-nona to a solution prepared by mixing 3 parts of methyl difluoro (fluorosulfonyl) acetic acid and 26 parts of dichloroethane. Fluorohexanol and 0.03 parts of sulfuric acid were added and the resulting mixture was stirred at reflux for 2 hours. The reaction mixture obtained was cooled to room temperature and 100 parts of ion-exchanged water was added thereto and then extracted with 100 parts of chloroform. The obtained organic layer was washed three times with water and then concentrated under reduced pressure to obtain 5.3 parts of the compound represented by the formula (t).

(2) To a solution prepared by dissolving 1.5 parts of trifluoroacetophenone oxime in 2.5 parts of N, N-dimethylformamide, 0.9 parts of 2,6-lutidine and 3.7 parts of the compound represented by the formula (t) are added. It was. The resulting mixture was stirred at rt for 18 h. To the obtained reaction mixture, saturated aqueous ammonium chloride solution was added, and then the obtained mixture was extracted with ethyl acetate. The organic layer obtained was washed with ion-exchanged water and then concentrated under reduced pressure. The obtained residue was purified by silica gel chromatography to obtain 3.0 parts of the compound represented by the formula (u), which is referred to as B12.

Example 15

To a solution prepared by dissolving 4.0 parts of 2-trifluoroacetonaphtone oxime in 12 parts of N, N-dimethylformamide, 2.2 parts of 2,6-lutidine and 7.4 parts of the compound represented by the formula (a) were added. It was. The resulting mixture was stirred for 16 hours at room temperature. To the obtained reaction mixture, saturated aqueous ammonium chloride solution was added, and then the obtained mixture was extracted with ethyl acetate. The organic layer obtained was washed with ion-exchanged water and then concentrated under reduced pressure. The obtained residue was purified by silica gel chromatography to obtain 4.5 parts of the compound represented by the formula (v), which is called B13.

Example 16

To a solution prepared by mixing 5 parts of the compound represented by the formula (h) and 25 parts of chloroform, 4.3 parts of 12-hydroxydodecyl methacrylate, 0.01 parts of p-methoxyphenol and 0.19 parts of titanium triisopropoxide Was added and the resulting mixture was stirred at reflux for 22 h. The reaction mixture obtained was cooled to room temperature and 6 parts of silica gel was added thereto. The resulting mixture was stirred for 30 minutes and then filtered. The filtrate obtained was concentrated under reduced pressure. To the obtained residue, extraction was performed by adding n-heptane and ion-exchanged water. The organic layer obtained was washed three times with ion-exchanged water and then concentrated under reduced pressure. The obtained residue was purified by silica gel chromatography to obtain 3.6 parts of the compound represented by the formula (w), which is referred to as B14.

The monomers used in the examples below are the following monomers E1, E2, E3, E4, E5 and E6.

Example 17

In a four-necked flask equipped with a condenser, a stirrer and a thermometer, 4.65 parts of 1,4-dioxane was added, and then heated to 77 ° C. 4.0 parts B8, 1.7 parts monomer E1, 0.02 parts 2,2'-azobisisobutyronitrile, 0.11 parts 2,2'-azobis (2,4-dimethylvaleronitrile) and 8.1 parts 1,4-di The solution prepared by mixing oxane was added drop wise over 2 hours. The resulting mixture was heated at 77 ° C. for 5 hours. The reaction mixture was cooled to room temperature and then poured into a mixed solution of 13.3 parts water and 53.1 parts methanol to precipitate. The precipitate was separated and washed with methanol and dried under reduced pressure to give a resin having a weight-average molecular weight of 9,600 and a degree of dispersion (Mw / Mn) of 2.6. This resin had the following structural units. This is called Resin D1.

Example 18

To a four-necked flask equipped with a condenser, a stirrer and a thermometer, 7.4 parts of 1,4-dioxane was added, and then heated to 77 ° C. 4.5 parts B8, 4.1 parts monomer E2, 0.05 parts 2,2'-azobisisobutyronitrile, 0.22 parts 2,2'-azobis (2,4-dimethylvaleronitrile) and 4.6 parts 1,4-di The solution prepared by mixing oxane was added drop wise over 2 hours. The resulting mixture was heated at 77 ° C. for 5 hours. The reaction mixture was cooled to room temperature and then poured into a mixed solution of 21.5 parts water and 85.9 parts methanol to precipitate. The precipitate was separated and washed with methanol and dried under reduced pressure to give a resin having a weight-average molecular weight of 6,800 and a degree of dispersion (Mw / Mn) of 1.7. This resin had the following structural units. This is called Resin D2.

Example 19

To a four-necked flask equipped with a condenser, a stirrer and a thermometer, 3.9 parts of 1,4-dioxane was added, and then heated to 72 ° C. 5.7 parts B8, 7.4 parts monomer E2, 0.08 parts 2,2'-azobisisobutyronitrile, 0.37 parts 2,2'-azobis (2,4-dimethylvaleronitrile) and 15.7 parts 1,4-di The solution prepared by mixing oxane was added drop wise over 2 hours. The resulting mixture was heated at 72 ° C. for 5 hours. The reaction mixture was cooled to room temperature and then poured into a mixed solution of 34 parts water and 136 parts methanol to precipitate. The precipitate was separated and washed with methanol and dried under reduced pressure to obtain a resin having a weight-average molecular weight of 12,000 and a degree of dispersion (Mw / Mn) of 1.8. This resin had the following structural units. This is called Resin D3.

Example 20

To a four-necked flask equipped with a condenser, a stirrer and a thermometer, 3.9 parts of 1,4-dioxane was added, and then heated to 68 ° C. 9.2 parts B8, 3.9 parts monomer E2, 0.04 parts 2,2'-azobisisobutyronitrile, 0.16 parts 2,2'-azobis (2,4-dimethylvaleronitrile) and 15.7 parts 1,4-di The solution prepared by mixing oxane was added drop wise over 2 hours. The resulting mixture was heated at 68 ° C. for 5 hours. The reaction mixture was cooled to room temperature and then poured into a mixed solution of 34 parts water and 136 parts methanol to precipitate. The precipitate was separated and washed with methanol and dried under reduced pressure to give a resin having a weight-average molecular weight of 31,000 and a degree of dispersion (Mw / Mn) of 2.1. This resin had the following structural units. This is called Resin D4.

Example 21

To a four-necked flask equipped with a condenser, a stirrer, and a thermometer, 3.5 parts of 1,4-dioxane were added, and then heated to 76 ° C. 10.3 parts B8, 1.5 parts monomer E2, 0.1 parts 2,2'-azobisisobutyronitrile, 0.45 parts 2,2'-azobis (2,4-dimethylvaleronitrile) and 14.2 parts 1,4-di The solution prepared by mixing oxane was added drop wise over 2 hours. The resulting mixture was heated at 76 ° C. for 5 hours. The reaction mixture was cooled to room temperature and then poured into a mixed solution of 31 parts water and 123 parts methanol to precipitate. The precipitate was separated and washed with methanol and dried under reduced pressure to give a resin having a weight-average molecular weight of 12,000 and a degree of dispersion (Mw / Mn) of 1.9. This resin had the following structural units. This is called Resin D5.

Example 22

To a four-necked flask equipped with a condenser, a stirrer, and a thermometer, 8.3 parts of 1,4-dioxane were added, and then heated to 72 ° C. Prepared by mixing 27.6 parts B8, 0.1 parts 2,2'-azobisisobutyronitrile, 0.45 parts 2,2'-azobis (2,4-dimethylvaleronitrile) and 33.1 parts 1,4-dioxane Solution was added dropwise over 2 hours. The resulting mixture was heated at 72 ° C. for 5 hours. The reaction mixture was cooled to room temperature and then poured into a mixed solution of 72 parts water and 287 parts methanol to precipitate. The precipitate was separated and washed with methanol and dried under reduced pressure to give a resin having a weight-average molecular weight of 22,000 and a degree of dispersion (Mw / Mn) of 2.1. This resin had the following structural units. This is called Resin D6.

Example 23

To a four-necked flask equipped with a condenser, a stirrer and a thermometer, 7.5 parts of 1,4-dioxane was added and then heated to 68 ° C. 4.5 parts B8, 7.9 parts monomer E3, 0.2 parts 2,2'-azobisisobutyronitrile, 0.09 parts 2,2'-azobis (2,4-dimethylvaleronitrile) and 11.2 parts 1,4-di The solution prepared by mixing oxane was added drop wise over 2 hours. The resulting mixture was heated at 68 ° C. for 5 hours. The reaction mixture was cooled to room temperature and then poured into a mixed solution of 32 parts water and 130 parts methanol to precipitate. The precipitate was separated and washed with methanol and dried under reduced pressure to give a resin having a weight-average molecular weight of 19,000 and a degree of dispersion (Mw / Mn) of 1.9. This resin had the following structural units. This is called Resin D7.

Example 24

To a four-necked flask equipped with a condenser, a stirrer and a thermometer, 7.9 parts of 1,4-dioxane was added, and then heated to 73 ° C. 3.0 parts B8, 4.0 parts monomer E6, 0.7 parts monomer E2, 2.1 parts monomer E4, 3.7 parts monomer E5, 0.09 parts 2,2'-azobisisobutyronitrile, 0.41 parts 2,2'-azobis (2, 4-dimethylvaleronitrile) and 7.9 parts of 1,4-dioxane were mixed dropwise over 2 hours. The resulting mixture was heated at 73 ° C. for 5 hours. The reaction mixture was cooled to room temperature and then poured into a mixed solution of 34 parts water and 137 parts methanol to precipitate. The precipitate was separated and washed with methanol and dried under reduced pressure to give a resin having a weight-average molecular weight of 6,900 and a degree of dispersion (Mw / Mn) of 2.2. This resin had the following structural units. This is called Resin D8.

Example 25

Resin was prepared in the same manner as in Example 17, except that B14 was used instead of B8. This resin has the following structural units. This is called D9.

Example 26

Resin was prepared in the same manner as in Example 18 except that B14 was used instead of B8. This resin has the following structural units. This is called D10.

Example 27

A resin was prepared according to the same method as in Example 19 except that B14 was used instead of B8. This resin has the following structural units. This is called D11.

Example 28

A resin was prepared according to the same method as in Example 20 except for using B14 instead of B8. This resin has the following structural units. This is called D12.

Example 29

A resin was prepared according to the same method as in Example 21 except that B14 was used instead of B8. The resin has the following structural units. This is called D13.

Example 30

A resin was prepared according to the same method as in Example 22 except that B14 was used instead of B8. The resin has the following structural units. This is called Resin D14.

Example 31

A resin was prepared in the same manner as in Example 23 except that B14 was used instead of B8. This resin has the following structural units. This is called Resin D15.

Example 32

Resin was prepared in the same manner as in Example 24 except that B14 was used instead of B8. This resin has the following structural units. This is called Resin D16.

Example 33

A resin was prepared according to the same method as in Example 17 except that B7 was used instead of B8. This resin has the following structural units. This is called Resin D17.

Example 34

A resin was prepared according to the same method as in Example 18 except that B7 was used instead of B8. This resin has the following structural units. This is called Resin D18.

Example 35

A resin was prepared according to the same method as in Example 19 except that B7 was used instead of B8. This resin has the following structural units. This is called Resin D19.

Example 36

Resin was prepared in the same manner as in Example 20 except that B7 was used instead of B8. This resin has the following structural units. This is called Resin D20.

Example 37

A resin was prepared according to the same method as in Example 21 except that B7 was used instead of B8. This resin has the following structural units. This is called Resin D21.

Example 38

A resin was prepared according to the same method as in Example 22 except that B7 was used instead of B8. This resin has the following structural units. This is called Resin D22.

Example 39

A resin was prepared according to the same method as in Example 23 except that B7 was used instead of B8. This resin has the following structural units. This is called Resin D23.

Example 40

Resin was prepared in the same manner as in Example 24 except that B7 was used instead of B8. This resin has the following structural units. This is called Resin D24.

Reference Resin Synthesis Example 1

To a four-necked flask equipped with a condenser, a stirrer, and a thermometer, 25.3 parts of 1,4-dioxane was added, and then heated to 75 ° C. 7.9 parts Monomer E6, 15.1 parts Monomer E4, 5.1 parts Monomer E5, 0.16 parts 2,2'-azobisisobutyronitrile, 0.75 parts 2,2'-azobis (2,4-dimethylvaleronitrile) and 16.9 A solution prepared by mixing negative 1,4-dioxane was added dropwise thereto over 2 hours. The resulting mixture was heated at 75 ° C. for 5 hours. The reaction mixture was cooled to room temperature and then poured into a mixed solution of 73 parts water and 292 parts methanol to precipitate. The precipitate was separated and washed with methanol and dried under reduced pressure to obtain a resin having a weight-average molecular weight of 9,200 and a degree of dispersion (Mw / Mn) of 1.8. This resin had the following structural units. This is called Resin A1.

Reference Material Synthesis Example 2

To a four-necked flask equipped with a condenser, a stirrer, and a thermometer, 29.6 parts of 1,4-dioxane was added, and then heated to 73 ° C. 12.8 parts Monomer E1, 6.0 parts Monomer E2, 16.0 parts Monomer E3, 3.1 parts Monomer E4, 11.5 parts Monomer E5, 0.36 parts 2,2'-Azobisisobutyronitrile, 1.62 parts 2,2'-Azobis (2 , 4-dimethylvaleronitrile) and 44.4 parts of 1,4-dioxane were added dropwise over 2 hours. The resulting mixture was heated at 73 ° C. for 5 hours. The reaction mixture was cooled to room temperature and then poured into a mixed solution of 128 parts water and 514 parts methanol to precipitate. The precipitate was separated and washed with methanol and dried under reduced pressure to give a resin having a weight-average molecular weight of 8,900 and a degree of dispersion (Mw / Mn) of 1.6. This resin had the following structural units. This is called Resin A2.

Examples 41 to 46 and Comparative Example 1

<Acid generator>

B1, B2, B3, B4, B9, B10

C1:

<Quancher>

Q1: 2,6-diisopropylaniline

<Solvent>

Y1: 100 parts of propylene glycol monomethyl ether acetate

2-heptanone 20part

20 parts propylene glycol monomethyl ether

γ-butyrolactone 10part

The following components were mixed and dissolved, and further filtered through a fluorine resin filter having a pore diameter of 0.2 μm to prepare a resist composition.

Resin (Types and amounts listed in Table 1)

Acid generators (types and amounts listed in Table 1)

Quencher (Types and amounts listed in Table 1)

Solvent (Types are listed in Table 1)

The silicon wafers were each coated with "ARC-29A-8", which is an organic anti-reflective coating composition available from Nissan Chemical Industries, and then baked at 205 ° C. for 60 seconds, yielding a 780 mm-thick organic anti- A reflective coating was formed. Each of the resist compositions prepared as described above was spin-coated on an anti-reflective coating, so that the thickness of the resulting film was 0.15 탆 after drying. Silicon wafers thus coated with individual resist liquids were prebaked on a proximity hotplate at 100 ° C. for 60 seconds. Using an ArF excimer stepper (" FPA-5000AS3 ", NA = 0.75, 2/3 Annular, manufactured by Canon Inc.), each wafer formed in this manner together with a separate resist film was used in a line and space pattern. space pattern), and the exposure dose was changed step by step.

After exposure, each wafer was post-exposure baked on a hotplate at 100 ° C. for 60 seconds and then paddle development for 15 seconds using an aqueous solution of 2.38 wt% tetramethylammonium hydroxide at 23 ° C.

Each dark field pattern developed on the organic anti-reflective coating substrate after development was observed with a scanning electron microscope ("S-4100" manufactured by Hitachi, Ltd.), and the results are shown in Table 2. As used herein, the term "dark field pattern" includes a chromium base surface (light-shielding portion) and linear glass layers (light-transmitting portion) formed on the chromium surface and aligned with each other. It means a pattern obtained by exposure and development through a reticle. Thus, in the dark field pattern, after exposure and development, a resist layer surrounding the line and space pattern remains on the substrate.

Effective Sensitivity (ES): This is expressed as the exposure amount from which a line pattern and a space pattern can be obtained.

Pattern Profile: Each pattern developed on the organic anti-reflective coating substrate after development, which was obtained at the exposure dose of the ES. If the cross-sectional shape of the pattern is rectangular, the pattern profile is excellent and its evaluation is indicated by "O", and if the cross-sectional shape of the pattern is tapered, the pattern profile is bad and its evaluation is " X ".

Example number Resin (Type / Quantity) Acid Generator (Type / Quantity) Quencher (Type / Quantity) menstruum Example 41 A1 / 10 B1 / 2.00 Q1 / 0.01 Y1 Example 42 A1 / 10 B2 / 2.00 Q1 / 0.01 Y1 Example 43 A1 / 10 B3 / 1.23 Q1 / 0.01 Y1 Example 44 A1 / 10 B4 / 1.00 Q1 / 0.01 Y1 Example 45 A1 / 10 B9 / 2.00 Q1 / 0.01 Y1 Example 46 A1 / 10 B10 / 2.00 Q1 / 0.01 Y1 Comparative Example 1 A1 / 10 C1 / 1.69 Q1 / 0.03 Y1

Example number Pattern profile Example 41 O Example 42 O Example 43 O Example 44 O Example 45 O Example 46 O Comparative Example 1 X

Example 47

A resist composition was prepared in the same manner as in Example 46, except that B5 was used as the acid generator instead of B1. A pattern is obtained according to the same method as in Example 46, except that the resist composition comprising B5 is used instead of the resist composition comprising B1.

Example 48

A resist composition was prepared in the same manner as in Example 46, except that B6 was used as the acid generator instead of B1. A pattern was obtained according to the same method as in Example 46, except that a resist composition comprising B6 was used instead of a resist composition comprising B1.

Example 49

A resist composition was prepared in the same manner as in Example 46, except that B7 was used as the acid generator instead of B1. A pattern is obtained according to the same method as in Example 46, except that the resist composition comprising B7 is used instead of the resist composition comprising B1.

Example 50

A resist composition was prepared in the same manner as in Example 46, except that B8 was used as the acid generator instead of B1. A pattern is obtained in the same manner as in Example 46, except that the resist composition comprising B8 is used instead of the resist composition comprising B1.

Example 51

A resist composition was prepared in the same manner as in Example 46, except that B11 was used as the acid generator instead of B1. A pattern is obtained according to the same method as in Example 46, except that a resist composition comprising B11 is used instead of a resist composition comprising B1.

Example 52

A resist composition was prepared in the same manner as in Example 46, except that B12 was used as the acid generator instead of B1. A pattern is obtained according to the same method as in Example 46, except that a resist composition comprising B12 is used instead of a resist composition comprising B1.

Example 53

A resist composition was prepared in the same manner as in Example 46, except that B13 was used as the acid generator instead of B1. A pattern is obtained according to the same method as in Example 46, except that a resist composition comprising B13 is used instead of a resist composition comprising B1.

Example 54

A resist composition was prepared in the same manner as in Example 46, except that B13 was used as the acid generator instead of B1. A pattern is obtained according to the same method as in Example 46, except that a resist composition comprising B13 is used instead of a resist composition comprising B1.

Example 55

10 parts of Resin A1 and 2 parts of Resin D1 were dissolved in a mixture of 200 parts of propylene glycol monomethyl ether acetate, 35 parts of 2-heptanone and 3.5 parts of γ-butyrolactone. The resulting solution was filtered through a fluorine resin filter having a pore diameter of 0.2 μm to prepare a resist composition.

The silicon wafer was coated with “ARC-29A-8”, which is an organic anti-reflective coating composition available from Nissan Chemical Industries, and then baked at 205 ° C. for 60 seconds to produce 780 μs-thick organic anti-reflective A coating was formed. The thickness of the film obtained by spin-coating the resist composition prepared as described above on the anti-reflective coating was 0.15 탆 after drying. The silicon wafers thus coated with individual resist liquids were each prebaked on a proximity hotplate at 125 ° C. for 60 seconds each. Using an ArF excimer stepper (" FPA-5000AS3 " manufactured by Canon Inc., NA = 0.75, 2/3 annular), each wafer thus formed together with the individual resist film was exposed to a line and space pattern, and the exposure amount was changed stepwise. .

After exposure, each wafer was post-exposure baked on a hotplate at 125 ° C. for 60 seconds and then paddle developed for 15 seconds using an aqueous solution of 2.38 wt% tetramethylammonium hydroxide at 23 ° C.

The pattern developed on the organic anti-reflective coating substrate after development was observed with a scanning electron microscope ("S-4100" manufactured by Hitachi, Inc.), and as a result, a line width of 250 nm and a space of 250 nm at an effective sensitivity of 50 mJ / cm ² A resist pattern having a width was observed.

Example 56

A resist composition was prepared according to the same method as in Example 55 except that Resin D2 was used instead of Resin D1. A pattern was obtained according to the same method as in Example 55, except that the resist composition comprising the resin D2 was used instead of the resist composition comprising the resin D1.

Example 57

A resist composition was prepared according to the same method as in Example 55 except that Resin D3 was used instead of Resin D1. A pattern was obtained according to the same method as in Example 55 except that a resist composition comprising a resin D3 was used instead of a resist composition comprising a resin D1.

In the following examples, acid generator C2 represented by the following formula was used.

Example 58

10 parts of resin A2, 0.6 parts of resin D2, 1.5 parts of acid generator C2 and 0.122 parts of 2,6-diisopropylaniline were added to 250 parts of propylene glycol monomethyl ether acetate, 20 parts of propylene glycol monomethyl ether, 35 parts of 2-heptane And dissolved in a mixture of 3 parts of gamma -butyrolactone. The resulting solution was filtered through a fluorine resin filter having a pore diameter of 0.2 μm to prepare a resist composition.

The silicon wafer was coated with “ARC-29A-8”, which is an organic anti-reflective coating composition available from Nissan Chemical Industries, and then baked at 205 ° C. for 60 seconds to produce 780 μs-thick organic anti-reflective A coating was formed. The resist composition prepared as described above was spin-coated on an anti-reflective coating, so that the thickness of the film obtained was 0.08 μm after drying. The silicon wafers thus coated with individual resist liquids were each prebaked on a near hotplate at 85 ° C. for 60 seconds. Using an ArF excimer stepper (" FPA-5000AS3 " manufactured by Canon Inc., NA = 0.75, 2/3 annular), each wafer thus formed together with the individual resist film was exposed to a line and space pattern, and the exposure amount was changed stepwise. .

After exposure, each wafer was post-exposure baked on a hotplate at 85 ° C. for 60 seconds and then paddle developed for 15 seconds using an aqueous solution of 2.38 wt% tetramethylammonium hydroxide at 23 ° C.

The pattern developed on the organic anti-reflective coating substrate after development was observed with a scanning electron microscope ("S-4100" manufactured by Hitachi, Inc.), and as a result, a line width of 85 nm and a space of 85 nm at an effective sensitivity of 31 mJ / cm ² . A resist pattern having a width was observed.

Example 59

A resist composition was prepared in the same manner as in Example 58 except that Resin D3 was used instead of Resin D2. A line width of 85 nm and a space width of 85 nm were obtained at an effective sensitivity of 30 mJ / cm ² according to the same method as in Example 58, except that the resist composition comprising the resin D3 was used instead of the resist composition comprising the resin D2. The resist pattern which had was observed.

Example 60

A resist composition was prepared in the same manner as in Example 58 except that Resin D5 was used instead of Resin D2. A line width of 85 nm and a space width of 85 nm were obtained at an effective sensitivity of 30 mJ / cm ² according to the same method as in Example 58, except that the resist composition comprising the resin D5 was used instead of the resist composition comprising the resin D2. The resist pattern which had was observed.

Example 61

A resist composition was prepared in the same manner as in Example 58 except that Resin D6 was used instead of Resin D2. A line width of 85 nm and a space width of 85 nm were obtained at an effective sensitivity of 30 mJ / cm ² according to the same method as in Example 58, except that a resist composition comprising resin D6 was used instead of a resist composition comprising resin D2. The resist pattern which had was observed.

Example 62

A resist composition was prepared in the same manner as in Example 58 except that Resin D7 was used instead of Resin D2. A line width of 85 nm and a space width of 85 nm were obtained at an effective sensitivity of 29 mJ / cm ² according to the same method as in Example 58, except that the resist composition comprising the resin D7 was used instead of the resist composition comprising the resin D2. The resist pattern which had was observed.

Example 63

As in Example 58, except that Resin D8, D9, D10, D11, D12, D13, D14, D15, D16, D17, D18, D19, D20, D21, D22, D23, or D24 is used instead of Resin D2 According to the same method, a resist composition is prepared. Resisting a resist composition comprising resins D8, D9, D10, D11, D12, D13, D14, D15, D16, D17, D18, D19, D20, D21, D22, D23, or D24 in place of the resist composition comprising resin D2 Except that, a resist pattern can be observed in the same manner as in Example 58.

Example 64

10 parts of resin A2, 0.3 parts of resin D3, 0.3 parts of resin D6, 1.5 parts of acid generator C2 and 0.122 parts of 2,6-diisopropylaniline were added 250 parts of propylene glycol monomethyl ether acetate, 20 parts of propylene glycol monomethyl ether, It was dissolved in a mixture of 35 parts 2-heptanone and 3 parts γ-butyrolactone. The resulting solution was filtered through a fluorine resin filter having a pore diameter of 0.2 μm to prepare a resist composition.

A line width of 85 nm and 85 nm at an effective sensitivity of 30 mJ / cm ² according to the same method as in Example 58, except that a resist composition comprising Resin D3 and Resin D6 was used instead of a resist composition comprising Resin D2. A resist pattern having a space width was observed.

Example 65

10 parts of resin A2, 0.5 parts of resin D3, 1.5 parts of acid generator C2 and 0.055 parts of 2,6-diisopropylaniline were added to 220 parts of propylene glycol monomethyl ether acetate, 20 parts of propylene glycol monomethyl ether, 35 parts of 2-heptane And dissolved in a mixture of 3 parts of gamma -butyrolactone. The resulting solution was filtered through a fluorine resin filter having a pore diameter of 0.2 μm to prepare a resist composition.

The silicon wafer was coated with “ARC-29SR”, which is an organic anti-reflective coating composition available from Nissan Chemical Industries, and then baked at 205 ° C. for 60 seconds to produce a 930 Å-thick organic anti-reflective coating. Formed. The thickness of the film obtained by spin-coating the resist composition prepared as described above on an anti-reflective coating was 100 nm after drying. Silicon wafers thus coated with individual resist liquids were prebaked on a close hotplate at 115 ° C. for 60 seconds. Using an ArF excimer stepper (" XT: 1900Gi " manufactured by ASML, NA = 1.30, c-quad,? OUTER = 0.985,? INNER = 0.895), the wafer thus formed together with the individual resist film was exposed to a line and space pattern, and the exposure dose Changed in stages.

After exposure, the wafer was post-exposure baked on a hotplate at 85 ° C. for 60 seconds and then paddle developed for 21 seconds using an aqueous solution of 2.38 wt% tetramethylammonium hydroxide at 23 ° C.

The pattern developed on the organic anti-reflective coating substrate after development was observed with a scanning electron microscope ("S-4800" manufactured by Hitachi, Inc.), and as a result, a line width of 40 nm and a space of 40 nm at an effective sensitivity of 23 mJ / cm ² . A resist pattern having a width was observed.

Example 66

10 parts of resin A2, 0.1 parts of resin D4, 1.5 parts of acid generator C2 and 0.122 parts of 2,6-diisopropylaniline were added to 275 parts of propylene glycol monomethyl ether acetate, 20 parts of propylene glycol monomethyl ether, 35 parts of 2-heptane And dissolved in a mixture of 3 parts of gamma -butyrolactone. The resulting solution was filtered through a fluorine resin filter having a pore diameter of 0.2 μm to prepare a resist composition.

The silicon wafer was coated with “ARC-29SR”, which is an organic anti-reflective coating composition available from Nissan Chemical Industries, and then baked at 205 ° C. for 60 seconds to produce a 930 Å-thick organic anti-reflective coating. Formed. The thickness of the film obtained by spin-coating the resist composition prepared as described above on an anti-reflective coating was 100 nm after drying. The silicon wafers thus coated with individual resist liquids were prebaked on a proximity hotplate at 85 ° C. for 60 seconds. Using an ArF excimer stepper (" XT: 1900Gi " manufactured by ASML, NA = 1.35, annular, sigma OUTER = 0.9, sigma INNER = 0.675), the wafer thus formed together with the individual resist film was exposed to the line and space pattern. It was changed in stages.

After exposure, the wafer was post-exposure baked on a hotplate at 85 ° C. for 60 seconds and then paddle developed for 32 seconds using an aqueous solution of 2.38 wt% tetramethylammonium hydroxide at 23 ° C.

The pattern developed on the organic anti-reflective coating substrate after development was observed with a scanning electron microscope ("S-4100" manufactured by Hitachi, Inc.), and as a result, a line width of 50 nm and a space of 50 nm at an effective sensitivity of 35 mJ / cm ² . A resist pattern having a width was observed.

Example 67

Resin D1, D2, D5, D6, D7, D8, D9, D10, D11, D12, D13, D14, D15, D16, D17, D18, D19, D20, D21, D22, D23, or D24 are used instead of Resin D3 Except that, a resist composition was prepared according to the same method as in Example 65. The resist composition comprising resins D1, D2, D5, D6, D7, D8, D9, D10, D11, D12, D13, D14, D15, D16, D17, D18, D19, D20, D21, D22, D23 or D24 A resist pattern can be obtained according to the same method as in Example 65, except that it is used instead of the resist composition including the resin D3.

The present oxime compounds and the present polymers are novel and useful as acid generators, and the present compositions comprising the present oxime compounds or the present polymers provide resist patterns with good pattern profiles and in particular ArF excimer laser lithography, KrF excimer laser Suitable for lithography and ArF immersion lithography.

Claims (21)

Oxime compound represented by formula (I):

Wherein Y represents an unsubstituted or substituted n-valent C6-C14 aromatic hydrocarbon group, n represents an integer from 1 to 6, R ¹ has a C1-C30 aliphatic hydrocarbon group, a C6-C14 aromatic hydrocarbon group, a C4-C10 heteroaromatic hydrocarbon group, a C1-C20 alkyl group having a C6-C14 aromatic hydrocarbon group, or a C4-C10 heteroaromatic hydrocarbon group C1-C20 alkyl group, and at least one methylene group of the aliphatic hydrocarbon group to be replaced with -O-, -S-, -CO-, -CO-O-, -SO ₂ -or -N (R ^c )- And an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a heteroaromatic hydrocarbon group, and an alkyl group are hydroxyl group, acryloyloxy group, methacryloyloxy group, halogen atom, cyano group, -OR ² , -CO Substitute at least one selected from the group consisting of -OR ² , -O-CO-OR ² , -O-CO-R ² , -SO ₂ -OR ² , -O-SO ₂ -R ² and -SO ₂ R ² Can be, R ² represents a linear or branched chain C 1 -C 20 aliphatic hydrocarbon group, wherein at least one methylene group is to be replaced with -O-, -S-, -CO-, -CO-O- or -N (R ^c )- And it may be substituted with at least one selected from the group consisting of hydroxyl group, acryloyloxy group and methacryloyloxy group, R ^c represents a hydrogen atom or a linear or branched chain C 1 -C 4 aliphatic hydrocarbon group, W represents -CO-O-, -CH ₂ O- or -CH ₂ O-CO-, Q ¹ and Q ² each independently represent a fluorine atom or a C1-C6 perfluoroalkyl group, Z represents a C1-C20 halogenated aliphatic hydrocarbon group, a C6-C14 halogenated aromatic hydrocarbon group, a cyano group, -CX ₂ -R ¹ or -CX ₂ -SO ₂ -R ¹ , and X represents a halogen atom or Represents a C1-C20 halogenated aliphatic hydrocarbon group. The method of claim 1, n is 1, the oxime compound characterized by the above-mentioned. The method of claim 1, Unsubstituted or substituted n-valent C6-C14 aromatic hydrocarbon groups are unsubstituted or substituted phenyl groups, unsubstituted or substituted naphthyl groups, unsubstituted or substituted biphenyl groups, unsubstituted or substituted anthryl An oxime compound characterized by being a group, an unsubstituted or substituted fluorenyl group or an unsubstituted or substituted phenanthryl group. The method of claim 1, Z is a C1-C20 halogenated aliphatic hydrocarbon group or a C6-C14 halogenated aromatic hydrocarbon group. The method of claim 1, Q ¹ and Q ² each independently represent a fluorine atom or a trifluoromethyl group. The method of claim 1, R ¹ represents a C1-C30 aliphatic hydrocarbon group, wherein one or more methylene groups may be replaced with —O—, —S— or —N (R ^c ) —, which is from a group consisting of hydroxyl groups and halogen atoms An oxime compound, characterized in that it can be substituted with at least one selected. The method of claim 1, R ¹ is a C1-C30 aliphatic hydrocarbon group wherein at least one methylene group is replaced with -CO-. The method of claim 1, R ¹ is a C1-C30 aliphatic hydrocarbon group having an acryloyloxy group or a methacryloyloxy group, and at least one methylene group of the aliphatic hydrocarbon group is -O-, -S-, -N (R ^c )-, An oxime compound characterized in that it can be replaced with -CO- or -CO-O-. The method of claim 1, An oxime compound represented by formula (I) is an oxime compound represented by formula (III):

Here, Y ¹ is a C1-C20 aliphatic hydrocarbon group having a phenyl group, acryloyloxy group or methacryloyloxy group which may be substituted with a C1-C20 aliphatic hydrocarbon group having an acryloyloxy group or a methacryloyloxy group. C1-C20 aliphatic having a biphenyl group, acryloyloxy group or methacryloyloxy group which may be substituted with a C1-C20 aliphatic hydrocarbon group having a naphthyl group, acryloyloxy group or a methacryloyloxy group which may be substituted Having a fluorenyl group which may be substituted with a C1-C20 aliphatic hydrocarbon group having an anthryl group, an acryloyloxy group or a methacryloyloxy group which may be substituted with a hydrocarbon group, or an acryloyloxy group or a methacryloyloxy group A phenanthryl group which may be substituted with a C1-C20 aliphatic hydrocarbon group, and at least one methylene group of a C1-C20 aliphatic hydrocarbon group ^{-O-, -S-, -N (R c} ) -, -CO- , or may be replaced by -CO-O-, R ^c is a hydrogen atom or a linear or branched chain C1-C4 aliphatic monovalent hydrocarbon group , Z ¹ represents a C1-C20 halogenated aliphatic hydrocarbon group or a C6-C14 halogenated aromatic hydrocarbon group, R ³ represents a C3-C30 monocyclic or polycyclic aliphatic hydrocarbon group, wherein one or more methylene groups can be replaced with -O- or -CO-, which can be substituted with a hydroxyl group, R ⁴ represents a single bond or a C 1 -C 20 divalent aliphatic hydrocarbon group, wherein one or more methylene groups can be replaced with —O—, —S— or —N (R ^c ) —. The method of claim 9, Y ¹ is a phenyl group, naphthyl group, biphenyl group, anthryl group, fluorenyl group or phenanthryl group, characterized in that the oxime compound. The method of claim 9, R ³ is a C3-C30 monocyclic or polycyclic aliphatic hydrocarbon group, wherein at least one methylene group is replaced with -CO-. The method of claim 1, An oxime compound represented by formula (I) is an oxime compound represented by formula (Va); rwl

Wherein Y ² is an unsubstituted or substituted phenyl group, an unsubstituted or substituted naphthyl group, an unsubstituted or substituted biphenyl group, an unsubstituted or substituted anthryl group, an unsubstituted or substituted fluorenyl group Or an unsubstituted or substituted phenanthryl group, Z ¹ represents a C1-C20 halogenated aliphatic hydrocarbon group or a C6-C14 halogenated aromatic hydrocarbon group, R ⁵ represents a C1-C30 divalent aliphatic hydrocarbon group, wherein one or more methylene groups can be replaced with -O-, -S- or -N (R ^c )-, where R ^c is a hydrogen atom or a linear or branched A chain C1-C4 aliphatic hydrocarbon group, R ⁶ represents a hydrogen atom or a methyl group, W represents -CO-O-, -CH ₂ O- or -CH ₂ O-CO-, and Q ¹ and Q ² each independently represent a fluorine atom or a C1-C6 perfluoroalkyl group. The method of claim 12, Q ¹ and Q ² are fluorine atoms and W is -CO-O-. The method of claim 12, R ⁵ is a C1-C20 divalent aliphatic hydrocarbon group wherein at least one methylene group can be replaced with -O-, -S- or -N (R ^c )-. A polymer comprising a structural unit derived from an oxime compound according to claim 12. The method of claim 15, The polymer, in addition to the structural unit derived from the oxime compound according to claim 12, comprises a structural unit having an acid-labile group. A resist composition comprising a resin and an oxime compound according to claim 1. A resist composition comprising a resin and a polymer according to claim 15. The method of claim 17 or 18, The resin is a resist composition which is insoluble or poorly soluble in aqueous alkali solution, but soluble in aqueous alkali solution by the action of acid, and comprising a structural unit having an acid-labile group. The method of claim 17 or 18, The resin is a resist composition, characterized in that it further comprises another acid generator (acid generator). A process for preparing an oxime compound represented by formula (I) comprising:

Wherein Y represents an unsubstituted or substituted n-valent C6-C14 aromatic hydrocarbon group, n represents an integer from 1 to 6, R ¹ has a C1-C30 aliphatic hydrocarbon group, a C6-C14 aromatic hydrocarbon group, a C4-C10 heteroaromatic hydrocarbon group, a C1-C20 alkyl group having a C6-C14 aromatic hydrocarbon group or a C4-C10 heteroaromatic hydrocarbon group C1-C20 alkyl group, and at least one methylene group of the aliphatic hydrocarbon group to be replaced with -O-, -S-, -CO-, -CO-O-, -SO ₂ -or -N (R ^c )- And an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a heteroaromatic hydrocarbon group, and an alkyl group are hydroxyl group, acryloyloxy group, methacryloyloxy group, halogen atom, cyano group, -OR ² , -CO Substitute at least one selected from the group consisting of -OR ² , -O-CO-OR ² , -O-CO-R ² , -SO ₂ -OR ² , -O-SO ₂ -R ² and -SO ₂ R ² Can be, R ² represents a linear or branched chain C 1 -C 20 aliphatic hydrocarbon group, wherein at least one methylene group is to be replaced with -O-, -S-, -CO-, -CO-O- or -N (R ^c )- And it may be substituted with at least one selected from the group consisting of hydroxyl group, acryloyloxy group and methacryloyloxy group, R ^c represents a hydrogen atom or a linear or branched chain C 1 -C 4 aliphatic hydrocarbon group, W represents -CO-O-, -CH ₂ O- or -CH ₂ O-CO-, Q ¹ and Q ² each independently represent a fluorine atom or a C1-C6 perfluoroalkyl group, Z represents a C1-C20 halogenated aliphatic hydrocarbon group, a C6-C14 halogenated aromatic hydrocarbon group, a cyano group, -CX ₂ -R ¹ or -CX ₂ -SO ₂ -R ¹ , and X represents a halogen atom or C1-C20 halogenated aliphatic hydrocarbon group, Compound represented by formula (VII) is:

Where Y, Z and n have the same meaning as described above, Reaction in the presence of a base with a compound represented by formula (VIII):

Where R ¹ , W, Q ¹ and Q ² have the same meanings as described above, and L represents a halogen atom.